WO2007088126A2

WO2007088126A2 - Coatings reparable by energy discharge

Info

Publication number: WO2007088126A2
Application number: PCT/EP2007/050641
Authority: WO
Inventors: Reinhold Schwalm; Nick Gruber; Lydie Tuchbreiter; Gabriele Dlugosch; Frank Völlinger
Original assignee: Basf Se
Priority date: 2006-02-03
Filing date: 2007-01-23
Publication date: 2007-08-09
Also published as: WO2007088126A3; EP1984417A2; US20090000519A1

Abstract

Coating compounds containing particular siloxanes and reparable by energy discharge, resulting coatings reparable by energy discharge, methods for producing and using same.

Description

Through energy input reparable coatings

description

The present invention relates to energy-recoverable Beschichtungsmas- sen containing certain siloxanes, thus obtained by energy input reparable coatings, as well as processes for their preparation and their use.

WO 96/10595 A1 describes self-healing coatings which contain urethane prepolymers which, inter alia, contain carbinol-terminated polyalkylsiloxane-xantiol segments as structural components. In particular, ethylene oxide- or propylene oxide-terminated siloxane diols are disclosed as structures. The siloxanediols used in the examples have about 12-13 Si-O groups.

Polyurethane based coatings are also used to heal scratches on glass. They make use of the flowability of polyurethanes in the film. Examples thereof for this US 4584229, EP 135404 A1, DE 2634816 and EP 635348 A1 called.

All previously described self-healing lacquer systems according to the prior art use only a physical residual flowability of a coating after curing to heal the resulting scratches again. However, a sufficiently high flowability of the coatings requires a low crosslinking density. This leads to unsatisfactory mechanical resistance, the z. B. do not meet the requirements for automotive applications in terms of scratch resistance or chemical resistance.

A true chemical self-healing of a coating is described only in EP 355 028 A. In this case, a lower lacquer layer contains an aromatic ketone, which on UV exposure or under the influence of sunlight causes the crosslinking of lower lacquer layers and thus causes an annealing of mechanical defects by the formation of new chemical bonds , A disadvantage here is the lack of selectivity in the formation of new crosslinking points, since the crosslinking in the coating can proceed and then leads to embrittlement.

The use of polysiloxanes to improve the scratch resistance of paints is known, for example, from US 5916992 and EP-B1 1204701.

A disadvantage of such polysiloxanes is that thereby no self-healing of laminations is made possible. Mono- and disiloxanes bearing one or two phenolic groups are known from US 3328450. The disadvantage of this is that no use of these compounds is described.

In the German patent application with the file number 10 2005 034213.2 and the filing date 19.07.2005 self-healing coatings are described, the self-healing is based on cleavage of rückspaltbaren reaction products of isocyanates. Siloxane-containing products are not disclosed.

The object of the present invention is to provide reparable coatings by energy input which are at least as scratch-resistant as the coatings known hitherto in the prior art and have improved reparability caused by energy input compared to comparable coatings.

The object is achieved by coating compositions containing as structural components

(A) at least one compound which has at least one silicon atom and at least one isocyanate-reactive group (Y) whose reaction product is more easily cleaved with isocyanate than the corresponding reaction product with a compound having primary hydroxyl groups, and optionally at least one further opposite Isocyanate-reactive group (Z), which is different from (Y), as well as

(B) at least one optionally blocked di- or polyisocyanate.

The cleavage of the bond between isocyanate groups and groups (Y) is carried out by introducing heat and / or high-energy radiation and / or by applying pressure, preferably by introducing heat and / or high-energy radiation and more preferably by introducing heat, for example thermally or by NIR radiation. Under the cleavage conditions, the groups (Y) and isocyanate groups are at least partially regressed and can be rejoined. The coating material is thereby more easily flowable in the split state than the coating, scratches can heal by bleeding of the lower-viscosity coating composition and crosslink the coating compound again after the introduction of energy by rejoining the bonds between the groups (Y) and isocyanate groups.

In this document, the term coating composition is understood to mean the uncured composition which contains coating medium (binder) and optionally pigment and / or other typical coatings additives. The coating is understood to mean the applied and dried and / or cured coating composition.

The term "readily cleavable" is understood here that the cleavage reaction of the reaction product in groups (Y) and isocyanate groups proceeds under the chosen reaction conditions at a rate which is faster than that of the cleavage of the corresponding reaction product with a compound having primary hydroxyl groups, especially methanol.

The compounds (A) according to the invention contain at least one, preferably at least two, isocyanate-reactive groups (Y) whose reaction product is readily cleavable with isocyanate, and optionally at least one further isocyanate-reactive group (Z).

In an alternative embodiment, compounds (A) may be a mixture of such compounds which contain in each case exclusively at least one, preferably at least two, isocyanate-reactive groups (Y), with those which are exclusively isocyanate-reactive groups (Z) contain.

In a further alternative embodiment, the compounds (A) may be those which each contain exactly one group (Y) and exactly one group (Z).

It is a particular advantage of such compounds (A) according to the invention, which contain at least one group (Y) and at least one group (Z) in a molecule that the back-split groups (Y) can not escape from the coating, since they still over Groups (Z) are connected to the isocyanate group-containing component (B).

Isocyanate-reactive groups (Y) whose reaction product is readily cleavable with isocyanate are those groups which are used to block isocyanate groups.

Such groups are described in D.A. Wicks, Z.W. Wicks, Progress in Organic Coatings, 36, 148-172 (1999), 41, 1-83 (2001) and 43, 131-140 (2001).

Preferred groups (Y) are phenols, imidazoles, triazoles, pyrazoles, oximes, N-hydroxyimides, hydroxybenzoic acid esters, secondary amines, lactams, CH-acidic cyclic ketones, malonic esters or alkyl acetoacetates.

Imidazolic groups as isocyanate-reactive groups, referred to herein for short as "imidazoles", are known, for example, from WO 97/12924 and EP 1591 17, triazoles from US 4482721, CH-acidic cyclic ketones are described, for example, in DE-A1 102 60 269, there in particular in paragraph [0008] and preferably in paragraphs [0033] to [0037], particularly preferably cyclopentanone-2 carboxylic acid esters and in particular cyclopentanone-2-carboxylic acid ethyl ester.

Preferred imidazoles are, for example, those imidazoles which, in addition to the free NH group, also contain a further functional group, such as e.g. -OH, -SH, -NH-R, - NH 2, -CHO, such as, for example, 4- (hydroxymethyl) imidazole, 2-mercapto-imidazole, 2-aminoimidazole, 1- (3-aminopropyl) imidazole, 4, 5-diphenyl-2-imidazolethiol, histamine, 2-imidazole-carboxaldehyde, 4-imidazole carboxylic acid, 4,5-imidazole-dicarboxylic acid, L-histidine, L-carnosine, and 2,2'-bis- (4,5-dimethyl imidazole).

Suitable triazoles are 3-amino-1, 2,4-triazole, 4-amino-1, 2,4-triazole, 3,5-diamino-1,2,4-triazole, 1H-1,2,4-triazole-3-thiol, 5 -Methyl-1H-1, 2,4-triazole-3-thiol and 3-amino-5-mercapto-1, 2,4-triazole.

Secondary amines are preferably tert-butyl benzylamine.

Preference is given to phenols, oximes, N-hydroxyimides, lactams, imidazoles, triazoles, malonic esters and alkylacetonates; particularly preferred are lactams, phenols, imidazoles, triazoles and malonic esters, and very particular preference is given to phenols.

The compounds (A) according to the invention contain on average at least one, preferably at least 2, more preferably 2 to 20, very preferably 2 to 10, in particular 2 to 6, especially 2 to 4, often 2 to 3 and even exactly 2 groups ( Y).

Groups (Y) may be present in compound (A) in amounts of up to 5 mol / kg of compound (A), preferably 0.1 to 5, more preferably 0.3 to 4.5, most preferably 0.5 to 4 and especially 1 to 3 mol / kg.

In addition, the compounds (A) may optionally contain at least one, for example one to six, preferably one to four, particularly preferably one to three, very particularly preferably one to two and in particular exactly one further isocyanate-reactive group (Z).

However, preference is given to compounds (A) which have no further groups (Z).

Groups (Z) are isocyanate-reactive groups other than the groups (Y). These may be, for example, primary hydroxy, secondary hydroxy, tertiary hydroxy, primary amino or mercapto groups, preferably primary hydroxy or primary amino groups and more preferably primary hydroxy groups. Primary hydroxy groups are hydroxy groups attached to a carbon atom connected to exactly one more carbon atom. Analogously, in the case of secondary hydroxyl groups, the carbon atom bound to it is correspondingly bonded to two and to tertiary hydroxyl groups having three carbon atoms.

The carbon atoms to which the hydroxy groups are bonded can be cycloaliphatic or aliphatic carbon atoms, ie be part of a cycloaliphatic ring system or a straight or branched chain, but not of an aromatic ring system.

Primary amino groups are amino groups which are connected via a carbon atom with exactly one substituent, that is, have exactly two hydrogen atoms connected to the nitrogen atom.

Furthermore, according to the invention, the compounds (A) have at least one silicon atom, preferably 1 to 50, particularly preferably 2 to 40, very particularly preferably 3 to 30, in particular 3 to 20, especially 4 to 10, even 4 to 8 and often 5 to 7 silicon atoms.

In the compounds (A), the silicon atoms in the form of silane groups, ie consisting of silicon and hydrogen atoms may be present, silicon-organic groups, ie consisting of silicon atoms, which are substituted with any alkyl, aryl or cycloalkyl groups or preferably in the form of siloxanes, ie containing at least one Si-O-Si group (siloxane bond), wherein the silicon atoms can then be substituted by any desired alkyl, aryl or cycloalkyl groups. Such structures are sometimes referred to as silicones, that is, as compounds in which silicon atoms are linked in a chain-like and / or netlike manner via oxygen atoms and the remaining valences of the silicon are saturated by hydrocarbon radicals.

Preferred compounds (A) are those obtainable by reacting at least one compound (A1) having at least one silicon atom and at least one Si-H group with at least one compound (A2) containing at least one group (Y) and carries at least one vinylic group.

Preferred compounds (A1) have 1 to 6, preferably 1 to 4, particularly preferably 1 to 3, very particularly preferably 1 to 3, in particular 1 to 2 and especially 2 Si-H groups. Preferred compounds (A1) have 1 to 50, preferably 2 to 40, particularly preferably 3 to 30, very particularly preferably 3 to 20, in particular 4 to 10, especially 4 to 8 and even 5 to 7 silicon atoms.

In a preferred embodiment, the compounds (A1) are at least one organic polysiloxane hydride of the formula (I)

has, in which

R ^{1 is} independently hydrogen, hydroxy (-OH), Ci - Ciβ-alkyl, Ce - Ci2-aryl, Cs - Ci2-cycloalkyl, Ci - cis-alkoxy or Ce - Ci2-aryloxy and

n is an integer from 0 to 100

can mean

wherein at least one of the groups R ^{1 is} hydrogen.

In compounds of the formula (I), preference is given to the ratio of groups R ¹ which are hydrogen to groups R ¹ which are not hydrogen, from 0.1: 1 to 10: 1.

The compounds (A1) are particularly preferably at least one organic polysiloxane hydride of the formula (II)

or formula (IM)

wherein

R ² independently of one another are hydroxy (-OH), C 1 -C 6 -alkyl, C 12 -C 12 -aryl, Cs-C 12- Cycloalkyl, C 1 -C 6 -alkoxy and C 6 -C 12 -aryloxy,

n is an integer from 0 to 50, m is an integer from 1 to 50, and p is an integer from 0 to 50

can mean.

In compounds of the formula (II) or (III), the ratio of hydrogen atoms bonded to silicon atoms to groups R ² is preferably 0.1: 1 to 10: 1.

Mean in it

C 1 -C 6 -alkyl, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, Tetradecyl, hetadecyl, octadecyl, 1, 1-dimethylpropyl, 1, 1-dimethylbutyl or 1, 1, 3,3-tetramethylbutyl.

C 1 -C 6 -alkoxy, for example methoxy, ethoxy, n-propyloxy, isopropoxy, n-butyloxy, isobutoxy, sec-butyloxy or tert-butyloxy.

C 6 -C 12 -aryl, for example phenyl, ToIyI, XyIyI, α-naphthyl, β-naphthyl, 4-diphenylyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methylnaphthyl, isopropylnaphthyl, 6 - Dimethylphenyl or 2,4,6-trimethylphenyl.

C 1 -C 12 -cycloalkyl, for example cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl or butylcyclohexyl.

Cβ - Ci2-aryloxy, for example, phenyloxy, o-, m- or p-tolyloxy.

R ¹ and R ² are preferably, independently of one another, hydroxyl, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy or C ₆ -C 12 -aryl, particularly preferably C 1 -C ₄ -alkyl or phenyl, very particularly preferably C 1 -C ₄ -alkyl.

Ci to C ₄ alkyl means in the context of this document methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert. Butyl, preferably methyl, ethyl, n-butyl or tert. Butyl, more preferably methyl or ethyl, and most preferably methyl.

n is preferably an integer from 1 to 50, particularly preferably from 1 to 30, very particularly preferably from 2 to 20, in particular from 2 to 10 and especially from 3 to 5, m is preferably an integer from 1 to 30, particularly preferably from 1 to 20, very particularly preferably from 1 to 10, in particular from 1 to 5 and especially m is 1 and

p is preferably an integer from 0 to 30, particularly preferably from 0 to 20, very particularly preferably from 0 to 10, in particular from 0 to 5 and especially p is 0.

Examples of polysiloxane anhydrides are 1, 1, 3,3-tetramethyl disiloxane, polysiloxane anhydrides, in which n is 3 or 4, which are commercially available under the trade name Masilwax® BASE from PPG Industries Inc.

Formulas (I), (II) and (IM) are schematic and it is not intended to indicate that the parts in parentheses are necessarily blocks, although blocks may be used where desired. In many cases, the compound is more or less random, especially when more than a few siloxane units are used, and when mixtures are used. In those instances where more than a few siloxane units are used and it is desired to form blocks, oligomers are first formed and then these are joined to form the block compound. By judicious choice of reactants, compounds having an alternating structure or blocks of alternating structure can be used.

The compounds of the formulas (I), (II) or (III) can therefore be alternating, random or block polymers, preferably random or block polymers and particularly preferably random polymers.

The compounds (A2) may preferably be those of the formula (IV)

Vin-R ⁴ -Y

wherein

Vin a vinyl group,

R ^{4 is} a single bond, an oxygen atom, a nitrogen atom, C 1 -C 20 -alkylene, C 6 -C 12 -arylene, C 3 -C 12 -cycloalkylene, or by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted Imino groups and / or by one or more - (CO) -, -O (CO) O-, - (NH) (CO) O-, -O (CO) (NH) -, -O (CO) - or - (CO) O groups interrupted C ₂ -C ₂ o-alkylene and

Y is a group (Y) mean.

Particular preference is given to compounds (A2) of the formula (V)

Vin-R ⁵ - C ₆ -C 12 -aryl-OH

wherein

Vin has the above meaning and R ^{5 is} a single bond, an oxygen atom, a nitrogen atom or C 1 -C 20 -alkylene,

wherein the radicals R ⁵ and -OH are each bonded to those carbon atoms of the C 6 -C 12 -arylene group which are part of the aromatic ring system.

Very particular preference is given to compounds (A2) of the formula (VI)

wherein Vin and R ^{5 have} the above meanings,

R ^{6 are} each independently of the same x identical or different radicals selected from the group consisting of hydroxy (-OH), C 1 -C 20 -alkyl, C 1 -C 20 -alkyloxy and C 1 -C 12 -aryloxy and

x is an integer from 0 to 4

mean.

Where C 1 -C 20 -alkylene is linear or branched alkylene, e.g. Methylene, 1, 2-ethylene, 1, 2 or 1, 3-propylene, 1, 2, 1, 3 or 1, 4-butylene, 1, 1-dimethyl-1, 2-ethylene, 1, 2 Dimethyl 1, 2-ethylene, 1, 5-pentylene, 1, 6-hexylene, 1, 8-octylene, 1, 10-decylene or 1, 12-dodecylene,

C 3 -C 12 -cycloalkylene, for example, cyclopropylene, cyclopentylene, cyclohexylene, cyclooctylene, cyclododecylene,

C 6 -C 12 -arylene, for example, 1, 2, 1, 3 or 1, 4-phenylene, tolylene, xylylene, 4,4'-biphenylene or naphthylene, and Vin is an α, β-unsaturated C =C double bond, preferably a vinyl group (-CH = CHb), prop-1-en-1-yl group (-CH = CH-CH ₃ ) or prop-1-en-2-one ylgruppe (H ₂ C = C (CH ₃ ) -), particularly preferably a vinyl group (-CH = CH ₂ ) or prop-1-en-1-ylgruppe (-CH = CH-CH ₃ ) and very particularly preferably a vinyl group (-CH = CH ₂ ).

R ⁴ and R ⁵ are each, independently of one another, preferably a single bond, an oxygen atom or C ₁ -C ₂ O-Al kylene, more preferably a single bond or C ₁ -C ₂ O-Al kylene and most preferably C ₁ -C ₂ O-Al kylene , In particular, R ⁴ and R ⁵ are each independently methylene.

R ⁶ is preferably hydroxy (-OH), _Ci-C2o-alkyl or Ci-C ₂ o-alkyloxy, more preferably _Ci-C2o-alkyl or Ci-C ₂ o-alkyloxy, most preferably methyl or Metho - xy and in particular methoxy.

x is preferably 0 or 1.

The radicals R ⁵ and OH in formula (VI) may be ortho, meta or para to one another, preferably ortho or para and particularly preferably ortho for x = 0 and para for x ≠ 0.

The radicals R ⁶ and OH in formula (VI) may be ortho, meta or para to each other, provided that the respective position is not occupied by the radical R ⁵ , preferably ortho.

Preferred compounds (A2) are o-, m- and p-allylphenol, eugenol (4-allyl-2-methoxyphenol) and isoeugenol (2-methoxy-4- (1'-propenyl) -phenol), particular preference is given to Allylphenol and eugenol (4-allyl-2-methoxyphenol), most preferably o-allylphenol.

Thus, the following compounds represent a preferred object of the present invention:

(IIa)

such as

wherein

R ² , R ⁴ , R ⁵ , R ⁶ , Y, n, m and x have the meanings listed above.

Typically, the preparation of the compounds (A) is carried out in the following manner. The compound (A2) or a mixture thereof is used in ambient temperature is added to a reaction vessel equipped with means for maintaining an inert gas cover, preferably nitrogen or argon. At the same time, about 25 to 75 ppm of sodium bicarbonate or metal acetate salt is added to inhibit possible undesired side reactions, such as those associated with acetone condensation via a propenyl ether group. The temperature is raised to about 75 ° C to about 80 ° C under an inert gas blanket, at which time about 5% of the silicon hydride-containing polysiloxane (A1) is added with stirring. A catalyst such as a transition metal, eg, nickel, nickel salts, iridium salts, and more preferably a Group VIII noble metal, more preferably chloroplatinic acid, is then added and the reaction allowed to exotherm to 95 ° C. The addition of the remaining portion of the silicon hydride-containing polysiloxane (A1) is completed when the reaction temperature is maintained at 80 to 85 ° C. The reaction can be monitored by infrared spectroscopy for the disappearance of the absorption band of the silicon hydride (Si-H: 2150 cm ^-1 ).

In addition to the binder component (A), at least one further component (B) which contains at least one optionally blocked di- or polyisocyanate is present in the coating composition according to the invention.

These may be monomers or oligomers of aromatic, aliphatic or cycloaliphatic diisocyanates, preferably of aliphatic or cycloaliphatic diisocyanates

The NCO functionality of such compounds is generally at least 1.8, and may be up to 8, preferably from 1.8 to 5 and more preferably from 2 to 4.

Suitable polyisocyanates are polyisocyanates containing isocyanurate groups, polyisocyanates containing uretinyl groups, polyisocyanates containing urethane groups or allophanate groups, polyisocyanates containing oxadiazinetrione groups or iminooxadiazinedione groups, uretonimine-modified polyisocyanates of straight-chain or branched C 4 -C 20 -alkylene diisocyanates, cycloaliphatic diisocyanates having a total of from 6 to 20 C atoms or aromatic diisocyanates having a total of 8 to 20 carbon atoms or mixtures thereof.

The diisocyanates are preferably isocyanates having 4 to 20 carbon atoms. Examples of customary diisocyanates are aliphatic diisocyanates, such as tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecylenediisocyanate, derivatives of lysine diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates, such as 1, 4-, 1 , 3- or 1,2-diisocyanatocyclohexane, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, 1- Isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane (isophorone diisocyanate), 1, 3- or 1, 4-bis (isocyanatomethyl) cyclohexane or 2,4- or 2,6-diisocyanato-1-methylcyclohexane and 3 (or 4), 8 (or 9) -bis (isocyanatomethyl) -tricyclo [5.2.1.0 ²⁶ ] decane isomer mixtures, and aromatic diisocyanates such as 2,4- or 2,6-toluene diisocyanate and their isomer mixtures, m - or p-

Xylylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane and their isomer mixtures, 1, 3 or 1, 4-phenylene diisocyanate, 1-chloro-2,4-phenylene diisocyanate, 1, 5-naphthylene diisocyanate, diphenylene-4,4 'diisocyanate, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 3-methyldi-phenylmethane-4,4'-diisocyanate, tetramethylxylylene diisocyanate, 1, 4-diisocyanatobenzene or diphenyl ether-4,4'-diisocyanate. There may also be mixtures of said diisocyanates.

There are also higher isocyanates with an average of more than 2 isocyanate groups in consideration. Triisocyanates such as triisocyanatononane, 2,4,6-triisocyanatotoluene, triphenylmethane triisocyanate or 2,4,4'-triisocyanato-diphenyl ether or the mixtures of di-, tri- and higher polyisocyanates which are suitable for example by phosgenation of corresponding aniline / formaldehyde are suitable for this purpose - Be obtained condensates and represent methylene bridges Polyphenylpolyiso- cyanate.

The usable di- and polyisocyanates preferably have a content of isocyanate groups (calculated as NCO, molecular weight = 42) of 10 to 60% by weight, based on the diisocyanate and polyisocyanate (mixture), preferably 15 to 60% by weight and particularly preferably 20 to 55 wt%.

Preference is given to aliphatic or cycloaliphatic, in the context of this document as (cyclo) aliphatically summarized, di- and polyisocyanates, e.g. the abovementioned aliphatic or cycloaliphatic diisocyanates, or mixtures thereof.

Particularly preferred are hexamethylene diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, very particularly preferred are isophorone diisocyanate and hexamethylene diisocyanate, particularly preferably hexamethylene diisocyanate.

Isophorone diisocyanate is usually present as a mixture, namely the cis and trans isomers, usually in the ratio of about 60:40 to 80:20 (w / w), preferably in the ratio of about 70:30 to 75:25 and most preferably in the ratio of about 75:25.

Dicyclohexylmethane-4,4'-diisocyanate may also be present as a mixture of the different cis and trans isomers. Aromatic isocyanates are those containing at least one aromatic ring system.

Cycloaliphatic isocyanates are those containing at least one cycloaliphatic ring system.

Aliphatic isocyanates are those which contain exclusively straight or branched chains, ie acyclic compounds.

For the present invention, both such di- and polyisocyanates can be used, which are obtained by phosgenation of the corresponding amines, as well as those which without the use of phosgene, d. H. after phosgene-free process, are produced. For example, EP-A-0 126 299 (USP 4 596 678), EP-A-126 300 (USP 4 596 679) and EP-A-355 443 (USP 5 087 739) may disclose (cyclo) aliphatic diisocyanates, e.g. such as 1, 6-hexamethylene diisocyanate (HDI), isomeric aliphatic diisocyanates having 6 carbon atoms in the alkylene radical, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane and 1-isocyanato-S-isocyanato-methyl-S.δ. δ-trimethylcyclohexane (isophorone diisocyanate or IPDI) are prepared by reacting the (cyclo) aliphatic diamines with, for example, urea and alcohols to (cyclo) aliphatic biscarbamic acid esters and their thermal cleavage into the corresponding diisocyanates and alcohols. The synthesis is usually carried out continuously in a cyclic process and optionally in the presence of N-unsubstituted carbamic acid esters, dialkyl carbonates and other by-products recycled from the reaction process. Di- or polyisocyanates obtained in this way generally have a very low or even non-measurable proportion of chlorinated compounds, which leads to favorable color numbers of the products.

In one embodiment of the present invention, the di- and polyisocyanates (B) have a total hydrolyzable chlorine content of less than 200 ppm, preferably less than 120 ppm, more preferably less than 80 ppm, most preferably less than 50 ppm, especially less than 15 ppm and especially less than 10 ppm. This can be measured, for example, by ASTM D4663-98. However, it is of course also possible to use diisocyanates and polyisocyanates (B) with a higher chlorine content.

Further to mention are

1) isocyanurate polyisocyanates of aromatic, aliphatic and / or cycloaliphatic diisocyanates. Particular preference is given here to the corresponding aliphatic and / or cycloaliphatic isocyanato-isocyanurates and in particular those based on hexamethylene diisocyanate and isophorone diisocyanate. The isocyanurates present are in particular tris-isocyanatoalkyl or tris-isocyanatocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologs having more than one isocyanurate ring. The isocyanato-isocyanurates generally have an NCO content of 10 to 30 wt .-%, in particular 15 to 25 wt .-% and an average NCO-

Functionality from 2.6 to 8.

2) uretdione diisocyanates having aromatic, aliphatic and / or cycloaliphatic bonded isocyanate groups, preferably aliphatically and / or cycloaliphatically bonded and in particular those derived from hexamethylene diisocyanate or isophorone diisocyanate. Uretdione diisocyanates are cyclic dimerization products of diisocyanates.

The uretdione diisocyanates can be used as the sole component or in a mixture with other polyisocyanates, in particular those mentioned under 1).

3) biuret-containing polyisocyanates having aromatic, cycloaliphatic or aliphatic bound, preferably cycloaliphatic or aliphatic bound isocyanate groups, in particular tris (6-isocyanatohexyl) biuret or mixtures thereof with its higher homologs. These biuret polyisocyanates generally have an NCO content of 18 to 22 wt .-% and an average NCO functionality of 2.8 to 4.5.

4) polyisocyanates containing urethane and / or allophanate groups with aromatically, aliphatically or cycloaliphatically bonded, preferably aliphatically or cycloaliphatically bonded isocyanate groups, as obtained, for example, by reacting excess amounts of hexamethylene diisocyanate or of isophorone diisocyanate with monohydric or polyhydric alcohols, e.g. Methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol). hol), 2-ethylhexanol, n-pentanol, stearyl alcohol, cetyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1,3-propanediol monomethyl ether, cyclopentanol, cyclohexanol, cyclooctanol, cyclododecanol, trimethylolpropane, neopentyl glycol, pentaerythritol, 1,4-butane -diol, 1, 6-hexanediol, 1, 3-propanediol, 2-ethyl-1, 3-propanediol, 2-methyl-1, 3-propanediol, ethylene glycol,

Diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, glycerol, 1,2-dihydroxypropane, 2,2-dimethyl-1,2-ethanediol, 1,2-butanediol, 1,4-butanediol, 3-methylpentan-1, 5-diol, 2-ethylhexane-1, 3-diol, 2,4-diethyloctane-1,3-diol, neopentyl glycol hydroxypivalate, ditrimethylolpropane, dipentaerythritol, 2,2-bis (4-hydroxycyclohexyl) propane, 1, 1-, 1, 2-, 1, 3- and 1, 4-cyclohexanedimethanol, 1, 2, 1, 3 or 1, 4-cyclohexanediol or mixtures thereof can be obtained. These polyethers containing urethane and / or allophanate groups isocyanates generally have an NCO content of 12 to 20 wt .-% and an average NCO functionality of 2.5 to 4.5.

5) oxadiazinetrione-containing polyisocyanates, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such oxadiazinetrione-containing polyisocyanates are accessible from diisocyanate and carbon dioxide.

6) polyisocyanates containing iminooxadiazinedione groups, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such iminooxadiazine-dione-containing polyisocyanates can be prepared from diisocyanates by means of special catalysts.

7) Uretonimine-modified polyisocyanates.

8) carbodiimide-modified polyisocyanates.

9) Hyperbranched polyisocyanates, as are known, for example, from DE-A1 10013186 or DE-A1 10013187.

10) polyurethane-polyisocyanate prepolymers, of di- and / or polyisocyanates with alcohols.

1 1) polyurea-polyisocyanate prepolymers.

The polyisocyanates 1) to 1 1) can be used in admixture, optionally also in admixture with diisocyanates.

The di- and polyisocyanates (B) may also be present at least partially in blocked form.

Such isocyanate blocking groups are described in D.A. Wicks, Z.W. Wicks, Progress in Organic Coatings, 36, 148-172 (1999), 41, 1-83 (2001) and 43, 131-140 (2001).

This is particularly preferred when the coating compositions according to the invention are to be used as one-component.

Preferred compounds (B) are the urethanes, biurets and isocyanurates, particularly preferably the isocyanurates of 1,6-hexamethylene diisocyanate (HDI) or 1-isocyanato-S-isocyanato-methyl-S.δ.δ-trimethyl-cyclohexane, very particularly preferably of 1-isocyanato-3-isocyanato-methyl-3,5,5-trimethyl-cyclohexane. As a result of the preparation, polyisocyanates (B) may still have a small proportion of the monomeric diisocyanate on which they are based, for example up to 5% by weight, more preferably up to 3% by weight, very preferably up to 2, in particular up to 1, especially up to 0.5 and even up to 0.25% by weight.

Furthermore, the coating compositions according to the invention generally also contain at least one binder (C) and optionally further co-crosslinkers (D) and / or paint-typical additives (E) and optionally pigments and / or fillers (F).

Preferred binders (C) are selected from the group consisting of polyethersols, polyesterols, polyacrylate polyols and melamine-formaldehyde resins, particularly preferably polyesterols and polyacrylate polyols and very particularly preferably polyacrylate polyols.

Polyester polyols are e.g. from Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 19, pp. 62-65. Polyester polyols are preferably used which are obtained by reacting dihydric alcohols with dibasic carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to prepare the polyesterpolyols. The polycarboxylic acids may be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic, and optionally, e.g. by halogen atoms, substituted and / or unsaturated. Examples include:

Oxalic, maleic, fumaric, succinic, glutaric, adipic, sebacic, dodecanedioic, o-phthalic, isophthalic, terephthalic, trimellitic, azelaic, 1,4-cyclohexanedicarboxylic or tetrahydrophthalic, hydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic anhydride, dimer fatty acids, their isomers and hydrogenation products and esterifiable derivatives, such as anhydrides or dialkyl esters, for example C 1 -C 4 -alkyl esters, preferably methyl, ethyl or n-butyl esters, of the acids mentioned become. Preference is given to dicarboxylic acids of the general formula HOOC- (CH 2) _y -COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, particularly preferably succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid.

Suitable polyhydric alcohols for the preparation of the polyesterols 1, 2-propanediol, ethylene glycol, 2,2-dimethyl-1, 2-ethanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 3-methylpentane-1, 5-diol, 2-ethylhexane-1,3-diol, 2,4- Diethyloctane-1,3-diol, 1,6-hexanediol, poly-THF having a molecular weight between 162 and 2000, poly-1,2-propanediol or poly-1,3-propanediol having a molecular weight between 134 and 10,000, preferably 134 to 5000, and more preferably 134 to 2000, or polyethylene glycol, and mixed polyethylene / propylene glycols as copolymers, wherein the 1, 2-ethylene and 1, 2-propylene units may be incorporated randomly or in blocks in the copolymer, with a molecular weight between 106 and 10,000, preferably 134 to 5000 and particularly preferably 134 to 2000, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, 2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-bis ( 4-hydroxycyclohexyl) propane, 1, 1-, 1, 2-, 1, 3- and 1, 4-cyclohexanedimethanol, 1, 2-, 1, 3- or 1, 4-cyclohexanediol, trimethylolbutane, trimethylolpropane, trimethylolethane, neopentyl glycol , Pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (Lyxite), XyNt, Dulcit (galactitol), maltitol, isomalt, tris (hydroxymethyl) isocyanurate or tris (hydroxyethyl) isocyanurate (THEIC). Of course, mixtures of the alcohols mentioned are also suitable.

Alcohols of the general formula HO- (CHa) _x -OH, where x is a number from 1 to 20, preferably an even number from 2 to 20, are preferred. Preferred are ethylene glycol, butane-1, 4-diol, hexane-1, 6-diol, octane-1, 8-diol and dodecane-1, 12-diol. Further preferred is neopentyl glycol.

Also included are polycarbonate diols, e.g. by reaction of phosgene with an excess of the mentioned as synthesis components for the polyester polyols low molecular weight alcohols, into consideration.

Also suitable are lactone-based polyesterdiols, which are homopolymers or copolymers of lactones, preferably terminal hydroxyl-containing addition products of lactones onto suitable difunctional starter molecules. Suitable lactones are preferably those which are derived from compounds of the general formula HO- (CH 2) Σ-COOH, where z is a number from 1 to 20 and an H atom of a methylene unit by a C 1 to C 4 alkyl radical may be substituted. Examples are ε-caprolactone, β-propiolactone, gamma-butyrolactone and / or methyl-ε-caprolactone, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid or pivalolactone and mixtures thereof. Suitable starter components are e.g. the low molecular weight dihydric alcohols mentioned above as the synthesis component for the polyesterpolyols. The corresponding polymers of ε-caprolactone are particularly preferred. Lower polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers. Instead of the polymers of lactones, it is also possible to use the corresponding, chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones.

The polyesters preferably have a determinable by gel permeation chromatography molecular weight M _n (number average) of 500 to 50,000, in particular 1,000 to 10,000 g / mol and a hydroxyl number of 16.5 to 264, preferably 33 to 200 mg KOH / g of solid resin.

The glass transition temperature T ₉ (DSC method (Differential Scanning Calorimetry) according to ASTM 3418/82) of these polyesters is preferably from -30 to 120 ° C.

Furthermore, polyacrylate polyols are preferred. These are generally copolymers of essentially (meth) acrylic esters, for example the C 1 -C 20 -alkyl (meth) acrylates listed above with the reactive diluents, with hydroxyalkyl (meth) acrylates, for example the mono (meth) acrylic acid esters from 1, 2-propanediol, ethylene glycol, 1, 3-propanediol, 1, 4-butanediol or 1, 6-hexanediol.

These preferably have a determinable by gel permeation chromatography molecular weight M _n (number average) of 500 to 50,000, in particular 1,000 to 10,000 g / mol and a hydroxyl number of 16.5 to 264, preferably 33 to 200 mg KOH / g of solid resin.

The glass transition temperature T ₉ (DSC method (Differential Scanning Calorimetry) according to ASTM 3418/82) of the polyacrylate is preferably -30 to 100 ⁰ C.

The hydroxyl-containing monomers are used in such amounts in the copolymerization that the above-mentioned hydroxyl numbers of the polymer sate result, which otherwise generally correspond to a hydroxyl group content of the polymers from 0.5 to 8, preferably 1 to 5 wt .-%. In general, the hydroxy-functional comonomers are used in amounts of 3 to 75, preferably 6 to 47 wt .-%, based on the total weight of the monomers used. In addition, of course, care must be taken that in the context of the information given, the amount of hydroxy-functional monomers is chosen so that copolymers are formed which have at least two hydroxyl groups per molecule on average.

The non-hydroxy-functional monomers include, for example, reactive diluents, ie compounds capable of free-radical or cationic polymerization with only one ethylenically unsaturated copolymerizable group.

Mention may be made, for example, of C 1 -C 20 -alkyl (meth) acrylates, vinylaromatics having up to 20 carbon atoms, vinyl esters of carboxylic acids containing up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl ethers of alcohols containing from 1 to 10 carbon atoms, β-unsaturated carboxylic acids and their anhydrides and aliphatic hydrocarbons fen with 2 to 8 carbon atoms and 1 or 2 double bonds.

Preferred (meth) acrylic acid alkyl esters are those having a C 1 -C 10 -alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.

In particular, mixtures of (meth) acrylic acid alkyl esters are also suitable.

Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are e.g. Vinyl laurate, vinyl stearate, vinyl propionate and vinyl acetate.

α, β-Unsaturated carboxylic acids and their anhydrides can be, for example, acrylic acid, methacrylic acid, fumaric acid, crotonic acid, itaconic acid, maleic acid or maleic anhydride, preferably acrylic acid.

As vinyl aromatic compounds are e.g. Vinyltoluene, α-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene into consideration.

Examples of nitriles are acrylonitrile and methacrylonitrile.

Suitable vinyl ethers are e.g. Vinyl methyl ether, vinyl isobutyl ether, vinyl hexyl ether and vinyl octyl ether.

As non-aromatic hydrocarbons having 2 to 8 carbon atoms and one or two olefinic double bonds may be mentioned butadiene, isoprene, and ethylene, propylene and isobutylene.

Furthermore, N-vinylformamide, N-vinylpyrrolidone and N-vinylcaprolactam can be used.

Preference is given to esters of acrylic acid or of methacrylic acid having 1 to 18, preferably 1 to 8, carbon atoms in the alcohol radical, such as e.g. Methyl acrylate. Ethyl acrylate, isopropyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-stearyl acrylate, the methacrylates corresponding to these acrylates, styrene, alkyl-substituted styrenes, acrylonitrile, methacrylonitrile, vinyl acetate or vinyl stearate or any desired mixtures of such monomers. Epoxide group-containing comonomers such as e.g. Glycidyl acrylate or methacrylate or monomers such as N-methoxymethylacrylamide or -methacrylamide can be used in small amounts.

The preparation of the polymers can be carried out by polymerization by conventional methods. The preparation of the polymers is preferably carried out in organic solution. Possible are continuous or discontinuous polymerization processes. Among the batch processes are the batch and feed processes to name, the latter being preferred. In the feed process, the solvent is introduced alone or with a part of the monomer mixture, heated to the polymerization temperature, the polymerization in the case of a monomer masterbatch started radically and the remaining monomer mixture together with an initiator mixture in the course of 1 to 10 hours, preferably 3 to 6 hours, added. Optionally, it is subsequently subsequently activated to carry out the polymerization to a conversion of at least 99%.

Examples of suitable solvents are aromatics such as solvent naphtha, benzene, toluene, xylene, chlorobenzene, esters such as ethyl acetate, butyl acetate, methyl glycol acetate, ethyl glycol acetate, methoxypropyl acetate, ethers such as butyl glycol, tetrahydrofuran, dioxane, ethyl glycol ethers, ketones such as acetone, methyl ethyl ketone, halogen-containing solvents such as Methylene chloride or trichloromonofluoroethane into consideration.

Preferred polyetherols are alkoxylated diols or polyols, particularly preferably the following stated diols or polyols in alkoxylated form:

Diols are, for example, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 1-dimethylethane-1, 2-diol, 2-butyl-2-ethyl-1, 3-propanediol, 2-ethyl-1, 3 Propanediol, 2-methyl-1, 3-propanediol, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, 1, 2, 1, 3 or 1, 4-butanediol, 1, 6-hexanediol, 1, 10-decanediol, bis (4- hydroxycyclohexane) isopropylidene, tetramethylcyclobutanediol, 1, 2-, 1, 3- or 1, 4-cyclohexanediol, cyclooctanediol, norbornanediol, pinanediol, decalindiol, 2-ethyl-1,3-hexanediol, 2,4-diethyl-octane 1, 3-diol, hydroquinone, bisphenol A, bisphenol F, bisphenol B, bisphenol S, 2,2-bis (4-hydroxycyclohexyl) propane, 1, 1, 1, 2, 1, 3 and 1, 4 Cyclohexanedimethanol, 1, 2, 1, 3 or 1, 4-cyclohexanediol.

Polyols are, for example, the abovementioned polyesterols, trimethylolbutane, trimethylolpropane, trimethylolethane, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xyNt, dulcitol ( Galactitol), maltitol or isomalt.

Preference is given to one to five times, more preferably three to five times and very particularly preferably four times ethoxylated, propoxylated or mixed ethoxylated and propoxylated and in particular exclusively ethoxylated glycerol, neopentyl glycol, trimethylolpropane, trimethylolethane or pentaerythritol.

For the alkoxylation suitable epoxidized olefins, for example, be ethylene oxide, propylene oxide, iso-butylene oxide, 1-butoxide, 2-butene oxide, vinyloxirane, styrene oxide and / or epichlorohydrin, preferably are ethylene oxide, propylene oxide, iso-butylene oxide, vinyloxirane, styrene oxide or epichlorohydrin, particularly preferably ethylene oxide and propylene oxide and very particularly preferably ethylene oxide. Alkoxylates may be random or block copolymers.

Further examples of polyetherols are polyTHF having a molecular weight between 162 and 2000, preferably between 162 and 1458, more preferably between 162 and 1098, most preferably between 162 and 738, and especially between 162 and 378, poly-1,3-propanediol and poly-1, 2-propanediol having a molecular weight between 134 and 1178, preferably between 134 and 888, more preferably between 134 and 598 and most preferably between 134 and 308, polyethylene glycol having a molecular weight between 106 and 898, preferably between 106 and 458, particularly preferably from 106 to 400, very particularly preferably between 106 and 235 and in particular diethylene glycol, triethylene glycol and tetraethylene glycol.

Furthermore, melamine-formaldehyde resins are suitable as binders. Such reactive groups include active methylol or alkylalkoxy groups, in particular methylalkoxy groups, and optionally imino groups (-NH-) on aminoplast crosslinkers, such as, for example, etherified reaction products of formaldehyde with amines, such as melamine, urea, etc., phenol / formaldehyde adducts , Siloxane or silane groups and anhydrides, such as in US Pat. No. 5,770,650.

Among the technically widespread and known, preferred aminoplasts are particularly preferred urea resins and melamine resins, such. Urea-formaldehyde resins, melamine-formaldehyde resins, melamine-phenol-formaldehyde resins or melamine-urea-formaldehyde resins, usable.

Suitable urea resins are those which are obtainable by reacting ureas with aldehydes and can be modified if appropriate.

As ureas, urea, N-substituted or N, N'-disubstituted ureas are suitable, e.g. N-methylurea, N-phenylurea, N, N'-dimethylurea, hexamethylenediurea, N, N'-diphenylurea, 1,2-ethylenediurea, 1,3-propylenediurea, diethylenetriurea, dipropylenetriurea, 2-hydroxypropylenediurea, 2- Imidazolidinone (ethyleneurea), 2-oxohexahydropyrimidine (propyleneurea) or 2-oxo-5-hydroxyhexahydropyrimidine (5-hydroxypropyleneurea).

Particularly suitable aldehydes are formaldehyde, acetaldehyde, isobutyraldehyde and glyoxal.

Urea resins may optionally be partially or completely modified, for example by reaction with mono- or polyfunctional alcohols, ammonia or amines (cationically modified urea resins) or with (hydrogen) sulfites (anionically modified urea resins). holmodified urea resins.

Possible alcohols for the modification are C 1 -C 6 -alcohols, preferably C 1 -C 4 -alkanols and, in particular, methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol and sec-butanol.

Suitable melamine resins are those which are obtainable by reacting melamine with aldehydes and which may optionally be partially or completely modified.

Melamine-formaldehyde resins are reaction products of the reaction of melamine with aldehydes, e.g. the o.g. Aldehydes, especially formaldehyde. Optionally, the resulting methylol groups are modified by etherification with the above-mentioned monohydric or polyhydric alcohols. Furthermore, the melamine-formaldehyde resins can also be modified as described above by reaction with amines, aminocarboxylic acids or sulfites.

By the action of formaldehyde on mixtures of melamine and urea or on mixtures of melamine and phenol, melamine-urea-formaldehyde resins or melamine-phenol-formaldehyde resins which can also be used according to the invention are also produced according to the invention.

The production of said aminoplasts is carried out according to known methods.

Particular examples are melamine-formaldehyde resins, including monomeric or polymeric melamine resins, and partially or fully alkylated melamine resins, urea resins, e.g. Methylolureas such as formaldehyde-urea resins, Al koxyharn substances such as butylated formaldehyde-urea resins, but also N-methylolacrylamide emulsions, iso-butoxy methyl acrylamide emulsions, such as Polyanhydri-. Polysuccinic anhydride, and siloxanes or silanes, e.g. Dimethyldimethoxysilanes.

Particularly preferred are aminoplast resins such as melamine-formaldehyde resins or formaldehyde-urea resins.

Typical melamine-formaldehyde resins have solids contents of from 50 to 97%, preferably from 60 to 96 and more preferably from 70 to 95%.

These melamine-formaldehyde resins are often dissolved in methanol, ethanol, n-butanol, isobutanol, xylene, butylglycol and / or water.

The viscosities at 23 ° C. are up to 10 Pas, preferably up to 7, especially preferably up to 6 Pas. Viscosities of 0.5 Pas are rarely fallen below.

The number average molecular weight Mn is generally from 250 to 1300, preferably from 300 to 1000 and particularly preferably from 300 to 450. The weight-average molecular weight is generally from 400 to 4200, preferably from 400 to 1700 and particularly preferably from 450 to 700 ,

The OH number according to DIN 53240-2 is generally from 40 to 1200 mg KOH / g.

The molar incorporation ratio of melamine: formaldehyde: alcohol is generally 1: 2 to 6: 1 to 6, preferably 1: 3 to 6: 2 to 6, and more preferably 1: 4 to 6: 3 to 5.5.

Co-crosslinkers (D) are compounds other than the diisocyanate and polyisocyanate (B), which can react with the binders (C) used.

Preferred co-crosslinkers (D) are compounds containing carbamate groups, which compounds are preferably used in particular if at least one melamine-formaldehyde resin is used as the binder.

Particularly preferred carbamate-containing compounds are tris (alkylcarbamoyl) triazines of the formula (VII)

wherein

R ⁹ , R ¹⁰ and R ¹¹ each independently of one another are C 1 -C 6 -alkyl, preferably C 1 -C ₄ -alkyl and particularly preferably methyl and / or n-butyl.

As further paint typical additives (E), for example, antioxidants, stabilizers, activators (accelerators), antistatic agents, flame retardants, thickeners, thixotropic agents, surface-active agents, viscosity modifiers, plasticizers or chelating agents can be used.

Suitable thickeners besides free-radically (co) polymerized (co) polymers, customary organic and inorganic thickeners such as hydroxymethylcellulose or bentonite. As chelating agents, for example, ethylenediamine-acetic acid and its salts and β-diketones can be used.

Suitable fillers include silicates, e.g. Example by hydrolysis of silicon tetrachloride available silicates such as Aerosil ^® the Fa. Degussa, silica, talc, aluminum silicates, magnesium silicates, calcium carbonates, etc.

Suitable stabilizers include typical UV absorbers such as oxanilides, triazines and benzotriazole (the latter available as Tinuvin ^® grades from Ciba-Spezialitatenchemie) and benzophenones. These may be used alone or together with suitable radical scavengers, for example sterically hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or derivatives thereof, eg. For example, bis (2,2,6,6-tetra-methyl-4-piperidyl) sebacinate can be used. Stabilizers are usually used in amounts of from 0.1 to 5.0% by weight, based on the solid components contained in the preparation.

The additives (E), insofar as they are solids, preferably have a particle size below 100 .mu.m and more preferably below 50 .mu.m.

In a particular embodiment, the additives (E), insofar as they are solids, preferably have a particle size of 1 to 1000 nm, particularly preferably 1 to 100 nm, very particularly preferably 5 to 50 nm and in particular 5 to 25 nm.

Such particles may be constituted as described in EP 1204701 B1, paragraphs [0032] to [0059], which is herewith part of the disclosure of this document.

The particles may be uniformly or non-uniformly distributed within the finished coating. In the case of an uneven distribution, the particles are preferably present on the surface of the coating in a higher concentration than in the interior of the coating.

Furthermore, the coating compositions may contain pigments, dyes and / or fillers (F).

Pigments are according to CD Römpp Chemie Lexikon - Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995 with reference to DIN 55943 particulate "practically insoluble in the application medium, inorganic or organic, colored or achromatic colorants". This distinguishes pigments from soluble dyes.

In this case, practically insoluble means a solubility at 25 ° C. of less than 1 g / 1000 g of application medium, preferably less than 0.5, more preferably less than 0.25, very preferably less than 0.1 and in particular less than 0.05 g / 1000 g of application medium. Examples of pigments include any systems of absorption and / or effect pigments, preferably absorption pigments. Number and selection of the pigment components are not subject to any restrictions. They can be adapted to the particular requirements, for example the desired color impression, as desired.

Effect pigments are to be understood as meaning all pigments which have a platelet-like structure and impart special decorative color effects to a surface coating. The effect pigments are, for example, all effect pigments which can usually be used in vehicle and industrial coating. Examples of such effect pigments are pure metal pigments; such as. Aluminum, iron or copper pigments; Interference pigments, such as z, B. titanium oxide coated mica, iron oxide coated mica, mixed oxide coated mica (e.g., with titanium dioxide and Fe2O3 or titanium dioxide and Cr2O3), metal oxide coated aluminum, or liquid crystal pigments.

The coloring absorption pigments are, for example, customary organic or inorganic absorption pigments which can be used in the coatings industry. Examples of organic absorption pigments are azo pigments, phthalocyanine, quinacridone and pyrrolopyrrole pigments. Examples of inorganic absorption pigments are iron oxide pigments and carbon black.

Furthermore, titanium dioxide is to be mentioned as a pigment.

Examples of pigments are listed in WO 97/08255, p. 8, Z. 11 to p. 11, Z. 16, which is hereby part of the disclosure of this document.

Typically, the coating compositions of the invention are composed as follows:

(A) from 0.1 to 80% by weight, preferably from 10 to 80% by weight,

(B) from 0.1 to 80% by weight, preferably from 10 to 80% by weight,

(C) from 0 to 99% by weight, preferably from 0 to 80% by weight, (D) from 0 to 50% by weight, preferably from 0 to 30% by weight,

(E) from 0 to 5% by weight, preferably from 0.1 to 5% by weight,

(F) from 0 to 60% by weight, preferably from 0.1 to 40% by weight,

with the proviso that the sum always gives 100% by weight.

The molar ratio of optionally blocked isocyanate groups in (B) to isocyanate-reactive groups in (A) and (C) in total is in the Rule 0.5: 1 to 2: 1, preferably 0.8: 1 to 1, 2: 1, more preferably 0.9: 1 to 1, 1: 1 and most preferably 0.95: 1 to 1, 05th :1.

The coating compositions according to the invention can be both one-component and two-component. Two-component means that the components (A) and (B) and optionally other coating constituents are mixed together only relatively shortly before the application and then essentially react with one another after application to the substrate. Mixing usually takes place in the case of two-component paints within a period of not more than 12 hours, preferably not more than 10, more preferably not more than 9, very preferably not more than 7, in particular not more than 5 and especially not more than 3 hours before application to the substrate.

In contrast, one-component (1 K) coating compositions can be mixed together longer before application.

The coatings obtained with the coating compositions of the invention generally have a glass transition temperature T ₉ above -30, preferably above -10 ° C. The upper limit is usually at glass transition temperatures T ₉ of not more than 120, preferably not more than 100 ° C (according to the DSC method (Differential Scanning Calorimetry) according to ASTM 3418/82).

In a further embodiment of the present invention, the coating compositions according to the invention are dual- or multi-cure-capable.

In the context of this document, the term "dual cure" or "multi-cure" refers to a hardening process which takes place via two or more than two mechanisms, for example selected from radiation, moisture, chemical, oxidative and / or thermal curing, preferably selected from radiation, moisture, chemical and / or thermal curing, particularly preferably selected from radiation, chemical and / or thermal curing and very particularly preferably radiation and chemical curing.

Radiation hardening in the sense of this document is defined as the polymerization of polymerisable compounds as a result of electromagnetic and / or particulate radiation, preferably UV light in the wavelength range of λ = 200 to 700 nm and / or electron radiation in the range of 150 to 300 keV and especially preferably with a radiation dose of at least 80, preferably 80 to 3000 mJ / cm ² .

Radiation-curing may preferably be carried out using free-radically polymerizable compounds, for example those selected from the group consisting of polyetherol (meth) acrylates, polyester resins, and the coating compositions according to the invention. ROL (meth) acrylates, epoxy (meth) acrylates, urethane (meth) acrylates and polycarbonate (meth) acrylates are added, and optionally as reactive diluent low-viscosity multifunctional (meth) acrylates which at least 1, preferably 2-10, particularly preferably 2-6, most preferably 2-4 and especially 2-3 (meth) acrylate groups, preferably carry acrylate groups.

The present invention further provides reaction products (G) of compounds (A) which have at least one, preferably at least two, isocyanate-reactive groups (Y) having at least one isocyanate compound having at least two, preferably at least two, isocyanate groups.

Such isocyanates may be monomers or oligomers of aromatic, aliphatic or cycloaliphatic diisocyanates, preferably of aliphatic or cycloaliphatic diisocyanates or polyisocyanates based on these diisocyanates.

Preference is given to isocyanurate, urethane or allophanate-containing polyisocyanates.

The diisocyanates are preferably isocyanates having 4 to 20 C-

Atoms. Examples of customary diisocyanates are aliphatic diisocyanates, such as tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecylenediisocyanate, derivatives of lysine diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates, such as 1, 4-, 1 , 3- or 1,2-diisocyanatocyclohexane, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, 1-isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane (isophorone diisocyanate), 1 , 3- or 1,4-bis (isocyanatomethyl) cyclohexane or 2,4- or 2,6-diisocyanato-1-methylcyclohexane and 3 (or 4), 8 (or 9) -bis (isocyanatomethyl) -tricyclo [5.2.1.0 ²⁶ ] decane isomer mixtures, and aromatic diisocyanates such as 2,4- or 2,6-toluene diisocyanate and their isomer mixtures, m- or p-xylylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane and their isomers - mixtures of 1, 3 or 1, 4-phenylene diisocyanate, 1-chloro-2,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, diphenyl-4,4'-diisocyanate, 4,4'-diisocyanato-3,3'- dimethyldiphenyl, 3-methyldi-phenylmethane-4,4'-diisocyanate, tetramethylxylylene diisocyanate, 1,4-diisocyanatobenzene or diphenyl ether-4,4'-diisocyanate. There may also be mixtures of said diisocyanates.

Preferred are aliphatic or cycloaliphatic, di- and polyisocyanates, e.g. the abovementioned aliphatic or cycloaliphatic diisocyanates, or mixtures thereof.

Isophorone diisocyanate is usually present as a mixture, namely the cis and trans isomers, usually in the ratio of about 60:40 to 80:20 (w / w), preferably in the ratio of about 70:30 to 75 : 25 and most preferably in the ratio of about 75:25.

Dicyclohexylmethane-4,4'-diisocyanate may also be present as a mixture of the different cis and trans isomers.

Aromatic isocyanates are those containing at least one aromatic ring system.

Cycloaliphatic isocyanates are those which contain at least one cycloaliphatic ring system. Aliphatic isocyanates are those which contain exclusively straight or branched chains, ie acyclic compounds.

Further to mention are

1) isocyanurate polyisocyanates of aromatic, aliphatic and / or cycloaliphatic diisocyanates. Particular preference is given here to the corresponding aliphatic and / or cycloaliphatic isocyanato-isocyanurates and in particular those based on hexamethylene diisocyanate and isophorone diisocyanate. The isocyanurates present are, in particular, trisisocyanatoalkyl or trisisocyanatocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologs having more than one isocyanurate ring. The isocyanato-isocyanurates generally have an NCO content of 10 to 30 wt .-%, in particular 15 to 25 wt .-% and an average NCO-

Functionality from 2.6 to 8.

2) uretdione diisocyanates having aromatic, aliphatic and / or cycloaliphatic bound isocyanate groups, preferably aliphatically and / or cycloaliphatically bonded and in particular those derived from hexamethylene diisocyanate or isophorone diisocyanate. Uretdione diisocyanates are cyclic dimerization products of diisocyanates.

4) polyisocyanates containing urethane and / or allophanate groups with aromatic, aliphatic or cycloaliphatic bound, preferably aliphatically or cycloaliphatically bonded isocyanate groups, as obtained, for example, by reacting excess amounts of hexamethylene diisocyanate or of isophorone diisocyanate with monohydric or polyhydric alcohols, for example methanol, Ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol) , 2-ethylhexanol, n-pentanol, stearyl alcohol, cetyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1,3-propanediol monomethyl ether, cyclopentanol, cyclohexanol, cyclooctanol, cyclododecanol, trimethylolpropane, neopentyl glycol, pentaerythritol, 1,4-butanediol, 1,6-hexanediol, 1,3-propanediol, 2-ethyl-1,3-propanediol, 2-methyl- 1, 3-propanediol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, glycerol, 1, 2-dihydroxypropane, 2,2-dimethyl-1,2-ethanediol, 1, 2-butanediol, 1, 4- Butanediol, 3-methylpentan-1, 5-diol, 2-ethylhexane-1,3-diol, 2,4-diethyloctane-1,3-diol, neopentyl glycol hydroxypivalate, ditrimethylolpropane, dipentaerythritol, 2,2-bis ( 4-hydroxycyclohexyl) propane, 1, 1, 1, 2, 1, 3 and 1, 4-cyclohexanedimethanol, 1, 2, 1, 3 or 1, 4-cyclohexanediol or Gemi see see can be. These urethane and / or allophanate-containing polyisocyanates generally have an NCO content of 12 to 20 wt .-% and an average NCO functionality of 2.5 to 4.5.

In a preferred embodiment, the alcohols are those which have a hydroxyl group and at least one (meth) acrylate group, for example 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate or pentaerythritol triacrylate.

Particular preference is given to those polyisocyanates containing allophanate groups, as described in WO 00/39183, there in particular of S. 4,

Z. 14 to S. 1 1, Z.1 and the compounds disclosed in the examples, which is hereby part of the disclosure of this document.

7) Uretonimine-modified polyisocyanates.

8) carbodiimide-modified polyisocyanates.

10) polyurethane-polyisocyanate prepolymers, of di- and / or polyisocyanates with alcohols. 1 1) polyurea-polyisocyanate prepolymers.

Preferred compounds (G) are those of the following formulas

(IXc)

(IXd) as well

(IXe)

O

(IXf)

wherein the radicals are as defined above and in addition

R ^{12 is} an aromatic, aliphatic or cycloaliphatic organic divalent radical comprising 2 to 20 carbon atoms

means.

Preferred radicals R ¹² are 1, 6-hexylene, 2,4-toluylene, 2,6-toluylene, isophorylene, 4,4'-bis (cyclohexyl) methan-ylen, particularly preferably 1, 6-hexylene.

Particular preference is given to compounds of the formula (IXg)

wherein

the radicals are as defined above and in addition

R ^{13 is} an aliphatic or cycloaliphatic divalent radical having 1 to 8 carbon atoms, R ^{14 is} hydrogen or methyl and q is a positive integer or random number fractional real number of at least 1,

mean.

Examples of R ¹³ are 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,1-dimethyl-1,2-ethylene, 1,4-butylene and 1,6-hexylene, preferably 1 , 2-ethylene, 1, 2-propylene, 1, 3-propylene and particularly preferred is 1, 2-ethylene.

R ¹⁴ is preferably hydrogen.

The value of q is preferably more than 1, particularly preferably more than 1 to 10, very particularly preferably more than 1 to 5, in particular more than 1 to 3 and especially more than 1 to 2.

Another object of the present invention are reaction products (H) of the compounds (G) described above with compounds containing at least one, preferably exactly one isocyanate-reactive group and at least one, preferably 1 to 6, particularly preferably 1 to 4, very particularly preferably have 1 to 3 radically polymerizable group.

Isocyanate-reactive groups can be, for example, -OH, -SH, -NH 2 and -NHR ¹⁵ , wherein R ^{15 is} hydrogen or an alkyl group containing 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl iso-butyl, sec-butyl or tert-butyl. Preferably, the isocyanate-reactive group is hydroxy (-OH) or amino (-NH 2), more preferably hydroxy (-OH).

Free-radically polymerizable groups are, for example, vinyl ether groups, acrylate or methacrylate groups, preferably acrylate or methacrylate groups and particularly preferably acrylate groups.

Such compounds may be, for example, monoesters of .alpha.,. Beta.-unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, acrylamidoglycolic acid, methacrylamidoglycolic acid or vinyl ethers with di- or polyols, which preferably have 2 to 20 C atoms and at least two hydroxy groups such as ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 1-dimethyl-1, 2-ethanediol, dipropylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, tripropylene glycol, 1, 2, 1, 3 or 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, 2-ethyl-1,4-butanediol, 1,4-dimethylolcyclohexane , 2,2-bis (4-hydroxycyclohexyl) propane, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, ditrimethylolpropane, erythritol, sorbitol, polyTHF with a molecular weight between 162 and 2000, poly-1,3-propanediol with a molecular weight between 134 and 400 or polyethylene glycol having a molecular weight between 238 and 458. Furthermore, esters or amides of (meth) acrylic acid with amino alcohols z. B. 2-aminoethanol, 2- (methylamino) - ethanol, 3-amino-1-propanol, 1-amino-2-propanol or 2- (2-aminoethoxy) ethanol, 2-mercaptoethanol or polyaminoalkanes, such as ethylenediamine or diethylenetriamine, or vinylacetic acid.

Preference is given to using 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1 , 6-hexanediol mono (meth) acrylate, glycerol mono- and di (meth) acrylate, trimethylolpropane mono- and di (meth) acrylate, pentaerythritol mono-, di- and tri (meth) acrylate and 4-hydroxybutyl vinyl ether, 2-aminoethyl (meth ) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 4-aminobutyl (meth) acrylate, 6-aminohexyl (meth) acrylate, 2-thioethyl (meth) acrylate, 2-aminoethyl (meth) acrylamide , 2-aminopropyl (meth) acrylamide, 3-aminopropyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, 2-hydroxypropyl (meth) acrylamide or 3-hydroxypropyl (meth) acrylamide. Particularly preferred are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate, 1, 4-butanediol monoacrylate, 3- (acryloyloxy) -2-hydroxypropyl (meth) acrylate and the monoacrylates of polyethylene glycol of molecular weight from 106 to 238.

Very particular preference is given to 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate, 1,4-butanediol monoacrylate and pentaerythritol triacrylate.

Preferred compounds (H) are those of the following formulas

b)

(Xc)

such as

(Xe)

(Xf)

wherein the radicals are as defined above and in addition

means.

Particular preference is given to compounds of the formula (Xg)

wherein the radicals are as defined above.

Another object of the present invention is the use of the compounds (G) in one- or two-component polyurethane coatings.

For use in one-component polyurethane coatings, it may be useful to block the isocyanate groups, for example with blocking agents as described above, preferably as described in DA Wicks, ZW Wicks, Progress in Organic Coatings, 36, 148-172 (1999 ), 41, 1-83 (2001) and 43, 131-140 (2001).

Another object of the present invention is the use of the compounds (H) in the radiation curing and in radiation-curable coatings.

Compounds which have both isocyanate- and free-radically polymerizable groups, such as, for example, compound (IXg), can advantageously be used in dual-cure curing.

Another object of the present invention are radiation-curable coating compositions comprising

at least one compound (H), if appropriate at least one compound having one or more than one free-radically polymerizable double bond, optionally at least one photoinitiator and, if appropriate, further typical lacquer additives.

The compounds (H) according to the invention can be used as the sole binder or, preferably, in combination with at least one further free-radically polymerizable compound.

Compounds having one or more than one free-radically polymerizable double bond are, for example, those compounds which have 1 to 6, preferably 1 to 4 and particularly preferably 1 to 3 free-radically polymerizable groups.

Free-radically polymerizable groups are, for example, vinyl ether or (meth) acrylate groups, preferably (meth) acrylate groups and particularly preferably acrylate groups.

Radically polymerizable compounds are often subdivided into monofunctional (compound having a radically polymerizable double bond) and multifunctional (compound having more than one radically polymerizable double bond), polymerizable compounds.

Monofunctional, polymerizable compounds are those having exactly one free-radically polymerizable group; multifunctional, polymerizable compounds are those having more than one, preferably having at least two free-radically polymerizable groups.

Monofunctional, polymerizable compounds are, for example, esters of (meth) acrylic acid with alcohols having 1 to 20 C atoms, for example (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid-2 ethylhexyl ester, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dihydrodicyclopentadienyl acrylate, vinylaromatic compounds, eg styrene, divinylbenzene, α, β-unsaturated nitriles, eg acrylonitrile, meth acrylonitrile, α, β-unsaturated aldehydes, for example acrolein, methacrolein, vinyl esters, for example vinyl acetate, vinyl propionate, halogenated ethylenically unsaturated compounds, for example vinyl chloride, vinylidene chloride, conjugated unsaturated compounds, for example butadiene, isoprene, chloroprene, monounsaturated compounds, for example Ethylene, propylene, 1-butene, 2-butene, isobutene, cyclic monounsaturated compounds, for example cyclopentene, cyclohexene, cyclododecene, N-vinylformamide, allylacetic acid ure, vinylacetic acid, monoethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms and their acid-soluble alkali metal, alkaline earth metal or ammonium salts such as, for example: acrylic acid, methacrylic acid, dimethylacrylic acid, ethacrylic acid, maleic acid, citraconic acid, methylenemalonic acid, crotonic acid, fumaric acid, mesaconic acid and itaconic acid, maleic acid, N-vinylpyrrolidone, N-vinyllactams, such as N, for example Vinylcaprolactam, N-vinyl-N-alkylcarboxamides or N-vinylcarboxamides, such as. As N-vinyl acetamide, N-vinyl-N-methylformamide and N-vinyl-N-methylacetamide or vinyl ethers, for example methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, iso-propyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, iso Butyl vinyl ether, tert-butyl vinyl ether, 4-hydroxy-butyl vinyl ether, and mixtures thereof.

Preferred among these are the esters of (meth) acrylic acid, particular preference is given to (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid n-butyl ester, (meth) acrylic acid 2-ethylhexyl ester and 2-hydroxyethyl acrylate, completely Particularly preferred are (meth) acrylic acid n-butyl ester, (meth) acrylic acid 2-ethylhexyl ester and 2-hydroxyethyl acrylate and especially 2-hydroxyethyl acrylate.

(Meth) acrylic acid in this specification stands for methacrylic acid and acrylic acid, preferably for acrylic acid.

Multifunctional, polymerizable compounds are preferably multifunctional (meth) acrylates which carry more than 1, preferably 2-10, more preferably 2-6, most preferably 2-4 and especially 2-3 (meth) acrylate groups, preferably acrylate groups.

These may be, for example, esters of (meth) acrylic acid with correspondingly at least dihydric polyhydric alcohols.

Such polyalcohols are, for example, at least divalent polyols, polyether or polyesterols or polyacrylate polyols having an average OH functionality of at least 2, preferably 3 to 10, suitable.

Examples of polyfunctional, polymerizable compounds are ethylene glycol diacrylate, 1,2-propanediol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,8 Octanediol diacrylate, neopentyl glycol diacrylate, 1, 1, 2, 1, 3 and 1, 4-cyclohexanedimethanol diacrylate, 1, 2, 1, 3 or 1, 4-cyclohexanediol diacrylate, trimethylolpropane triacrylate, ditri methylolpropane penta- or hexaacrylate, pentaerythritol tri- or tetraacrylate, glycerol di- or triacrylate, and di- and polyacrylates of sugar alcohols, such as sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xyNt, Dulcitol (galactitol), maltitol or isomalt, or of polyester polyols, polyetherols, polyTHF with a molecular weight between 162 and 2000, poly-1,3-propanediol with a molecular weight between see, 134 and 1178, polyethylene glycol having a molecular weight between 106 and 898, and epoxy (meth) acrylates, urethane (meth) acrylates or polycarbonate (meth) acrylates.

Further examples are (meth) acrylates of compounds of the formula (XIa) to (XId),

^H fxk ^ ^X t ^»

(XIa) (XIb) (XIc)

(XId)

wherein

R ¹⁶ and R ¹⁷ independently of one another denote hydrogen or C 1 -C 18 -alkyl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles,

k, I, r, s independently of one another each represent an integer from 1 to 10, preferably 1 to 5 and particularly preferably 1 to 3, and

each X, for i = 1 to k, 1 to I, 1 to r and 1 to s, may independently be selected from the group -CH ₂ -CH ₂ -O-, -CH ₂ -CH (CH ₃ ) -O -, -CH (CH ₃ ) -CH ₂ -O-, -CH ₂ --C (CHa) ₂ -O-, -C (CHa) ₂ -CH ₂ -O-, -CH ₂ -CHVin-O-, -CHVin-CH ₂ -O-, -CH ₂ -CHPh-O- and -CHPh-CH ₂ -O-, preferably from the group -CH ₂ -CH ₂ -O-, -CH ₂ -CH (CH ₃ ) -O- and -CH (CHa) -CH ₂ -O-, and more preferably -CH ₂ -CH ₂ -O-,

where Ph is phenyl and Vin is vinyl.

Therein Cis-alkyl which is optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles are, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl , Heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1, 1-dimethyl-propyl, 1, 1-dimethylbutyl, 1, 1, 3,3-tetramethylbutyl , preferably methyl, ethyl or n-propyl, very particularly preferably methyl or ethyl. These are preferably (meth) acrylates of one to twenty times and more preferably three to ten times ethoxylated, propoxylated or mixed ethoxylated and propoxylated and in particular exclusively ethoxylated glycerol, neopentyl glycol, trimethylolpropane, trimethylolethane or pentaerythritol.

Preferred multifunctional, polymerizable compounds are ethylene glycol diacrylate, 1,2-propanediol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, polyester polyol acrylates, polyetherol acrylates and triacrylate of one to twenty times alkoxylated, particularly preferably ethoxylated trimethylolpropane.

Very particularly preferred multifunctional, polymerizable compounds are 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate and triacrylate of one to twenty times ethoxylated trimethylolpropane.

Oxalic, maleic, fumaric, succinic, glutaric, adipic, sebacic, dodecanedioic, o-phthalic, isophthalic, terephthalic, trimellitic, azelaic, 1,4-cyclohexanedicarboxylic or tetrahydrophthalic, hydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic anhydride, dimer fatty acids, their isomers and hydrogenation products, and esterifiable derivatives such as anhydrides or dialkyl esters, for example C 1 -C 4 -alkyl esters, preferably methyl, ethyl or n-butyl esters, of the abovementioned Acids are used. Preference is given to dicarboxylic acids of the general formula HOOC- (CH 2) _y -COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, particularly preferably succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid.

Suitable polyhydric alcohols for preparing the polyesterols are 1, 2-propanediol, ethylene glycol, 2,2-dimethyl-1, 2-ethanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 3-methylpentane-1, 5-diol, 2-ethylhexane-1, 3-diol, 2,4-diethyloctane-1,3-diol, 1,6-hexanediol, polyTHF with a molecular weight between 162 and 2000, poly-1,3-propanediol with a molecular weight between 134 and 1178, poly-1,2 -propanediol having a molecular weight between 134 and 898, polyethylene glycol having a molecular weight of between 106 and 458, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, 2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-bis (4-hydroxycyclohexyl) propane, 1, 1, 1, 2, 1, 3 and 1, 4-cyclohexanedimethanol, 1, 2, 1, 3 or 1, 4-cyclohexanediol, trimethylolbutane, Trimethylolpropane, trimethylolethane, neopentyl glycol, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xyNt, dulcitol (galactitol), maltitol or isomalt, optionally as described above may be alkoxylated.

Also suitable are lactone-based polyesterdiols, which are homopolymers or copolymers of lactones, preferably terminal hydroxyl-containing addition products of lactones onto suitable difunctional starter molecules. Suitable lactones are preferably those which are derived from compounds of the general formula HO- (CH 2) Σ-COOH, where z is a number from 1 to 20 and an H atom of a methylene unit by a C 1 to C 4 alkyl radical may be substituted. Examples are ε-caprolactone, β-propiolactone, gamma-butyrolactone and / or methyl-ε-caprolactone, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid or pivalolactone and mixtures thereof. Suitable starter components are e.g. the low molecular weight dihydric alcohols mentioned above as the synthesis component for the polyesterpolyols. The corresponding polymers of ε-caprolactone are particularly preferred. Lower polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers. Instead of the polymers of lactones, it is also possible to use the corresponding, chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones. Furthermore, the multifunctional, polymerizable compound may be urethane (meth) acrylates, epoxy (meth) acrylates or carbonate (meth) acrylates.

Urethane (meth) acrylates are obtainable, for example, by reacting polyisocyanates with hydroxyalkyl (meth) acrylates or vinyl ethers and optionally chain extenders such as diols, polyols, diamines, polyamines or dithiols or polythiols. Urethane (meth) acrylates dispersible in water without the addition of emulsifiers additionally contain ionic and / or nonionic hydrophilic groups, which are introduced for example by structural components such as hydroxycarboxylic acids in the urethane.

Such urethane (meth) acrylates contain as structural components essentially:

(a) at least one organic aliphatic, aromatic or cycloaliphatic di- or polyisocyanate,

(B) at least one compound having at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group and

(C) optionally at least one compound having at least two isocyanate-reactive groups.

Components (a), (b) and (c) may be the same as described above for the polyurethanes of the invention.

The urethane (meth) acrylates preferably have a number average molecular weight M _n of 500 to 20,000, in particular of 500 to 10,000, more preferably 600 to 3000 g / mol (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard).

The urethane (meth) acrylates preferably have a content of 1 to 5, particularly preferably 2 to 4 moles of (meth) acrylic groups per 1000 g of urethane (meth) acrylate.

Epoxide (meth) acrylates are obtainable by reacting epoxides with (meth) acrylic acid. Suitable epoxides are, for example, epoxidized olefins, aromatic glycidyl ethers or aliphatic glycidyl ethers, preferably those of aromatic or aliphatic glycidyl ethers.

Epoxidized olefins may be, for example, ethylene oxide, propylene oxide, isobutylene oxide, 1-butoxide, 2-butene oxide, vinyl oxirane, styrene oxide or epichlorohydrin. Preferred are ethylene oxide, propylene oxide, isobutylene oxide, vinyl oxirane, styrene oxide or epichlorohydrin, particularly preferably ethylene oxide, propylene oxide or epichlorohydrin, and most preferably ethylene oxide and epichlorohydrin.

Aromatic glycidyl ethers are, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol B diglycidyl ether, bisphenol S diglycidyl ether, hydroquinone diglycidyl ether, alkylation products of phenol / dicyclopentadiene, for example 2,5-bis [(2, 3-E-epoxypropoxy) phenyl] octahydro-4,7-methano-5H-indene (CAS No. [13446-85-0]), Tris [4- (2,3-epoxypropoxy) phenyl] methane isomers) CAS-No. [66072-39-7]), phenol based epoxy novolacs (CAS # [9003-35-4]) and cresol based epoxy novolacs (CAS # [37382-79-9]).

Aliphatic glycidyl ethers are, for example, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, 1,1,2,2-tetrakis [4- (2,3-epoxypropoxy) phenyl] ethane (CAS No. [ 27043-37-4]), diglycidyl ethers of polypropylene glycol (α, ω-bis (2,3-epoxypropoxy) poly (oxypropylene) (CAS No. [16096-30-3]) and of hydrogenated bisphenol A (2 , 2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, CAS No. [13410-58-7]).

The epoxy (meth) acrylates and vinyl ethers preferably have a number average molecular weight Mn of from 200 to 20,000, particularly preferably from 200 to 10,000 g / mol and very particularly preferably from 250 to 3,000 g / mol; the content of (meth) acrylic or vinyl ether groups is preferably 1 to 5, more preferably 2 to 4 per 1000 g of epoxy (meth) acrylate or vinyl ether epoxide (determined by gel permeation chromatography with polystyrene as standard and tetrahydrofuran as eluent).

On average, carbonate (meth) acrylates preferably contain 1 to 5, in particular 2 to 4, particularly preferably 2 to 3 (meth) acrylic groups and very particularly preferably 2 (meth) acrylic groups.

The number average molecular weight M _{n of} the carbonate (meth) acrylates is preferably less than 3000 g / mol, more preferably less than 1500 g / mol, more preferably less than 800 g / mol (determined by gel permeation chromatography with polystyrene as standard, solvent tetrahydrofuran).

The carbonate (meth) acrylates are readily obtainable by transesterification of carbonic acid esters with polyhydric, preferably dihydric alcohols (diols, eg hexanediol) and subsequent esterification of the free OH groups with (meth) acrylic acid or transesterification with (meth) acrylic esters, as it eg in EP-A 92,269. They are also available by reacting phosgene, urea derivatives with polyvalent, e.g. dihydric alcohols.

Vinyl ether carbonates are also obtainable in an analogous manner by reacting a hydroxyalkyl vinyl ether with carbonic esters and optionally dihydric alcohols.

Also conceivable are (meth) acrylates or vinyl ethers of polycarbonate polyols, such as the reaction product of one of said diols or polyols and a carbonic acid ester and a hydroxyl-containing (meth) acrylate or vinyl ether. Suitable carbonic acid esters are, for example, ethylene, 1, 2 or 1, 3-propylene carbonate, carbonic acid dimethyl, diethyl or dibutyl ester.

Suitable hydroxyl-containing (meth) acrylates are, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, glycerol mono- and di (meth ) acrylate, trimethylol propane mono- and di (meth) acrylate and pentaerythritol mono-, di- and tri (meth) acrylate.

Suitable hydroxyl-containing vinyl ethers are e.g. 2-hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether.

Particularly preferred carbonate (meth) acrylates are those of the formula:

wherein R is H or CH3, X is a C2-C18 alkylene group and n is an integer from 1 to 5, preferably 1 to 3.

R is preferably H and X is preferably C 2 - to C 10 -alkylene, for example 1, 2-ethylene, 1, 2-propylene, 1, 3-propylene, 1, 4-butylene or 1, 6-hexylene, more preferably for C ₄ - to Cs-alkylene. Most preferably, X is Ce-alkylene.

The carbonate (meth) acrylates are preferably aliphatic carbonate (meth) acrylates.

Among the multifunctional polymerizable compound, urethane (meth) acrylates are particularly preferred.

Photoinitiators may be, for example, photoinitiators known to those skilled in the art, e.g. those in "Advances in Polymer Science", Volume 14, Springer Berlin 1974 or in K.K. Dietliker, Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints, Volume 3; Photoinitiators for Free Radical and Cationic Polymerization, P.K.T. Oldring (Eds), SITA Technology Ltd, London.

Suitable examples include mono- or Bisacylphosphinoxide, as described for example in EP-A 7 508, EP-A 57 474, DE-A 196 18 720, EP-A 495 751 or EP-A 615 980, for example, 2.4 , 6-trimethylbenzoyldiphenylphosphine oxide (Lucirin ^® TPO from BASF AG), ethyl 2,4,6-trimethylbenzoylphenylphosphinate (Lucirin ^® TPO L from BASF AG), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure® 819 from Ciba Specialty Chemicals), benzophenones, hydroxyacetophenones, phenylglyoxylic and their derivatives or mixtures of these photoinitiators. Examples which may be mentioned are benzophenone, acetophenone, acetonaphthoquinone, methyl ethyl ketone, valerophenone, hexanophenone, α-phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberone, 4-morpholinobenzophenone, 4-morpholinodeoxybenzoin, p-diacetylbenzene, 4-aminobenzophenone, 4'-methoxyacetophenone, β-methylanthraquinone, tert-butylanthraquinone, anthraquinone-carboxylic acid ester, benzaldehyde, α-tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 10-thioxanthenone, 3-acetylphenanthrene, 3-acetylindole, 9-fluorenone, 1 -lndanone, 1, 3,4-triacetylbenzene, thioxanthen-9-one, xanthen-9-one, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropyltrioxanthone, 2,4-dichlorothioxanthone , Benzoin, benzoin isobutyl ether, chloroxanthenone, benzoin tetrahydropyranyl ether, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, benzoin iso-propyl ether, 7-H-benzoin methyl ether, benz [de] anthracen-7-one , 1-naphthaldehyde, 4,4'-bis (dimethylamino) benzophenone, 4-phenylbenzophenone, 4-chloro-benz ophenone, Michler's ketone, 1-acetonaphthone, 2-acetonaphthone, 1-benzoylcyclohexan-1-ol, 2-hydroxy-2,2-dimethylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy 2-phenylacetophenone, 1, 1-dichloroacetophenone, 1-hydroxyacetophenone, acetophenone dimethyl ketal, o-methoxybenzophenone, triphenylphosphine, tri-o-tolylphosphine, benz [a] anthracene-7,12-dione, 2,2-diethoxyacetophenone, benzilene - talents such as benzil dimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone , 2-amylanthraquinone and 2,3-butanedione.

Also suitable are non-yellowing or slightly yellowing photoinitiators of the phenylglyoxalic acid ester type, as described in DE-A 198 26 712, DE-A 199 13 353 or WO 98/33761.

Preferred among these photoinitiators are 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphinate, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, benzophenone, 1-benzoylcyclohexan-1-ol , 2-hydroxy-2,2-dimethylacetophenone and 2,2-dimethoxy-2-phenylacetophenone.

The coating compositions according to the invention are particularly suitable for coating substrates such as wood, paper, textile, leather, fleece, plastic surfaces, glass, ceramics, mineral building materials, such as cement blocks and fiber cement boards, and in particular of metals or coated metals.

The coating of the substrates with the coating compositions according to the invention is carried out by customary methods known to the person skilled in the art, in which case a coating composition according to the invention or a coating formulation containing such applied to the substrate to be coated in the desired thickness and optionally dried. If desired, this process can be repeated one or more times.

The coating compositions may be prepared by a variety of application methods, such as e.g. Air pressure, airless or electrostatic spray method using one or two-component spray systems, but also by spraying, filling, doctoring, brushing, rolling, rolling, pouring, laminating, injection molding or coextrusion one or more times be applied.

The coating thickness is generally in a range of about 3 to 1000 g / m ² and preferably 10 to 200 g / m ² .

The drying and curing of the coatings is generally carried out under normal temperature conditions, i. without heating the coating. However, the mixtures according to the invention can also be used for the preparation of coatings which, after application at elevated temperature, e.g. at 40 - 250 ° C, preferably 40 - 150 ° C and especially at 40 to 100 ° C dried and cured. This is limited by the thermal stability of the substrate.

The drying and / or thermal treatment can also be carried out in addition to or instead of the thermal treatment by NIR radiation, wherein NIR radiation here electromagnetic radiation in the wavelength range of 760 nm to 2.5 microns, preferably from 900 to 1500 nm is designated.

The radiation curing is carried out with high-energy light, for example UV light or electron beams. The radiation curing can be carried out at higher temperatures. Preference is given to a temperature above the T _{9 of} the radiation-curable binder.

Radiation curing here means the free radical polymerization of polymerizable compounds due to electromagnetic and / or corpuscular radiation, preferably UV light in the wavelength range of λ = 200 to 700 nm and / or electron radiation in the range of 150 to 300 keV and more preferably with a radiation dose of at least 80, preferably 80 to 3000 mJ / cm ² .

Suitable radiation sources for radiation curing are, for example, low-pressure mercury lamps, medium-pressure lamps with high-pressure lamps and fluorescent tubes, pulse emitters, metal halide lamps, electronic flash devices, whereby a radiation curing without photoinitiator is possible, or Excimerstrahler. The radiation hardening is effected by the action of high-energy radiation, ie UV radiation or daylight, preferably emits light in the wavelength range of λ = 200 to 700 nm, more preferably of λ = 200 to 500 nm and most preferably λ = 250 to 400 nm, or by irradiation with high-energy electrons (electron radiation, 150 to 300 keV). The radiation sources used are, for example, high-pressure mercury vapor lamps, lasers, pulsed lamps (flash light), halogen lamps or excimer radiators. The radiation dose for UV curing, which is usually sufficient for crosslinking, is in the range from 80 to 3000 mJ / cm ² .

Of course, several radiation sources can be used for the curing, e.g. two to four.

These can also radiate in different wavelength ranges.

In addition to radiation curing, other curing mechanisms may be involved, for example thermal, moisture, chemical and / or oxidative curing (dual-cure).

For repair (self-healing) of the coatings according to the invention, the coatings are heated to a temperature of at least 10 minutes, preferably at least 15 minutes, preferably at least 20 minutes, more preferably at least 30, most preferably at least 45 and especially at least 60 minutes , which is at least 25, preferably at least 30 and more preferably at least 35 ° C above the glass transition temperature of the coating.

Such heating may be carried out by treatment at a corresponding temperature (for example in an oven or belt oven) or may additionally or exclusively also be carried out by heating with NIR radiation, in which case NIR radiation is electromagnetic radiation in the wavelength range from 760 nm to 2 , 5 μm, preferably from 900 to 1500 nm.

The coating compositions according to the invention can be used in particular as primers, fillers, pigmented topcoats and clearcoats in the field of industrial, in particular aircraft or large vehicle painting, wood, automotive, in particular OEM or automotive refinish, or decoration.

The compounds (A) lead in the coating compositions of the invention by the easy cleavability of the urethane groups formed by them to a self-healing effect in the coatings. The simultaneously containing silicon atoms, in particular siloxane groups, simultaneously increase the scratch resistance of the coatings.

The number of siloxane units is essential for optimizing the scratch resistance. If the number of siloxane units is too low, the scratch resistance is low. Therefore, at least three interconnected silicon siloxane bonds should be contained in atoms. From a certain upper limit of siloxane units no further improvement of the scratch resistance is more evident, so that a further increase in the number of silicon atoms no longer provides an advantage, but instead reduce the crosslink density of the bonding groups (Y). In addition, long siloxane units show marked incompatibilities (incompatibilities) with other coating components. Thus, up to 10 interconnected via siloxane bonds silicon atoms are usually sufficient.

Another object of the present invention is the use of compounds fertilize (A) as a reactant with di- and polyisocyanates and the reaction products thus obtained. The advantage of such reaction products is that they are easier to cleave back into the starting compounds than the corresponding reaction product with a compound having primary hydroxyl groups. Thus, such compounds (A) can be used as protecting groups for isocyanate group-containing compounds, especially di- and polyisocyanates (B). For this purpose, those compounds (A) are suitable which have only one or two silicon atoms, since it does not depend on the scratch resistance when used as protective groups.

Thus, in addition to the above-mentioned compounds (A), especially the compounds (A) obtainable by reacting at least one compound (A1) having at least one silicon atom and at least one Si-H group with at least one compound (A2) which bears at least one group (Y) and at least one vinylic group, and in particular those of the formulas (IIa), (IIb) and (IIIa) to (MId), also the following compounds of the formula (VIIIa) and (VIIIb) suitable:

(Villa)

(VIIIb)

wherein

R ² , R ⁴ , R ⁵ , R ⁶ , Y, n and x may have the abovementioned meanings.

Ppm and percentages used in this specification refer, unless otherwise indicated, to percentages by weight and ppm. The following examples are intended to illustrate but not to limit the invention.

Examples

example 1

In a three-necked flask with reflux condenser and stirrer, 123.15 g of eugenol (4-allyl-2-methoxyphenol) were added under inert gas to 1.70 mg of sodium bicarbonate with vigorous stirring. The original was heated to 75 ° C. Then, 8.70 g of DMS-H03 (hydride-terminated polydimethylsiloxane, Gelest, CAS No. 70900-21-9) and 0.52 ml of hexachloroplatinic acid hydrate (H ₂ [PtCl ₆ ], 1% solution in toluene were added / Isopropanol (1: 1)) as a catalyst. A weakly exothermic reaction was observed. Subsequently, the internal temperature was raised to 95 ° C and 165.30 g of DMS-H03 (hydride-terminated polydimethylsiloxane, Gelest, CAS 70900-21-9) was added dropwise within 60 minutes. The reaction mixture was stirred at 95 to 100 ° C for 90 minutes. The course of the reaction and the reaction conversion were monitored by infrared spectroscopy of the silicon hydride absorption band (Si-H, 2150 cm ^-1 ) The end product had an OH number to DIN 53240 of 138 mg KOH / g.

Example 2

In a three-necked flask with reflux condenser and stirrer, 107.34 g of 2-allylphenol were added under inert gas with vigorous stirring with 1.70 mg of sodium bicarbonate. The original was heated to 75 ° C. Then, 9.28 g of DMS-H03 (hydride-terminated polydimethylsiloxane, Gelest, CAS 70900-21-9) and 0.64 ml of hexachloroplatinic acid hydrate (H ₂ [PtCl], 1% strength solution in toluene / isopropanol (1 : 1)) as a catalyst. A weakly exothermic reaction was observed. The internal temperature was subsequently increased to 95 ° C., and 176.32 g of DMS-H03 (hydride-terminated polydimethylsiloxane, Gelest, CAS 70900-21-9) were added dropwise within 60 minutes. The reaction mixture was stirred at 95 to 100 ° C for 120 minutes. The course of the reaction and the reaction conversion were followed by infrared spectroscopy of the silicon hydride absorption band (Si-H, 2150 cm ^-1 ) The end product had an OH number to DIN 53240 of 149 mg KOH / g.

Example 3

A polyisocyanate containing allophanate groups was prepared from 1,6-hexamethylene diisocyanate and 2-hydroxyethyl acrylate analogously to Example 1 of WO 00/39183, so that a polyisocyanate having an NCO content after distillative removal of the unreacted monomeric 1,6-hexamethylene diisocyanate from 15.1% by weight (residual monomer content <0.5% by weight), a viscosity of 940 mPas at 23 ° C., an average molecular weight of about 800 g / mol and a double bond density of 2 mol / kg determined via ¹ H-NMR has been. The urethane acrylate thus obtained is referred to below as UA1.

In a three-necked flask with reflux condenser and stirrer were added to 207.31 g of urethane acrylate UA1 thus prepared 149.45 g siloxanediol (prepared according to Example 1), 0.20 g of methylhydroquinone and 0.40 g of 2,6-di-tert-butyl -p-cresol mixed at room temperature. 0.16 g of dibutyltin dilaurate were added as catalyst to the well-mixed template. This resulted in a slightly exothermic reaction, so that the internal temperature rose to about 30 ° C. The reaction mixture was stirred at 70 ° C until the NCO value of the reaction mixture was 5.18%. Then 42.64 g of hydroxyethyl acrylate were added dropwise within one hour. The reaction mixture was then stirred for two hours at 75 ° C internal temperature until the NCO value of the reaction mixture was 0.09%. The resulting urethane acrylate was diluted with 44.44 g of butyl acetate. The solids of the urethane acrylate was 88.0%. The double bond density of the solvent-free urethane acrylate was 2.1 mol / kg.

Example 4

In a three-necked flask with reflux condenser and stirrer were 213.20 g of urethane acrylate UA1 from Example 3, 142.35 g of siloxanediol (prepared according to Example 2), 0.20 g of methylhydroquinone and 0.40 g of 2,6-di-tert-butyl -p-cresol mixed at room temperature. 0.16 g of dibutyltin dilaurate were added as catalyst to the well-mixed template. This resulted in a slightly exothermic reaction, so that the internal temperature rose to about 30 ° C. The reaction mixture was stirred at 70 ° C until the NCO value of the reaction mixture was 4.43%. Then 43.85 g of hydroxyethyl acrylate were added dropwise within one hour. The reaction mixture was then stirred for three hours at 70 ° C internal temperature until the NCO value of the reaction mixture was 0.04%. The resulting urethane acrylate was with

Diluted 44.44 g of butyl acetate. The solids content of the urethane acrylate was 88.0%. The double bond density of the solvent-free urethane acrylate was 2.1 mol / kg.

Comparative Example 1

In a three-necked flask with reflux condenser and stirrer were 321, 85 g urethane acrylate UA1 from Example 3, 151, 22 g CAPA ^® 2054 (Polycaprolactondiol from Solvay, OH number = 21 1 mg KOH / g), 0.27 g Methylhydrochinon, 0 , 54 g of 2,6-di-tert-butyl-p-cresol and 59.92 g of butyl acetate mixed at room temperature. 0.22 g of dibutyltin dilaurate were added as catalyst to the well-mixed template. This resulted in a slightly exothermic reaction, so that the internal temperature rose to about 30 ° C. The reaction mixture was stirred at 70 ° C until the NCO value of the reaction mixture was 4.30%. Then 66.20 g 4.30%. Then 66.20 g of hydroxyethyl acrylate were added dropwise within one hour. The reaction mixture was then stirred for two hours at 70 ° C internal temperature until the NCO value of the reaction mixture was 0.02%. The resulting urethane acrylate was diluted with 35.30 g of butyl acetate. The solids of the urethane acrylate was 82.5%. The double bond density of the solvent-free urethane acrylate was 1.2 mol / kg.

Application test 1

Determination of the application properties Pendulum damping, Erichsen cupping and scratch resistance.

The determination of the pendulum damping was carried out analogously to DIN 53157. For this purpose, the radiation-curable compositions were applied with a wet film thickness of 400 microns on glass. The wet films were first flashed for 15 minutes at room temperature (23 ° C) and then dried at 100 ° C for 20 minutes. The curing of the films obtained in this way was carried out on an IST coating system (type M40 2x1 -R-IR-SLC-So inert) with 2 UV lamps (high-pressure mercury lamps type M 400 U2H and type M 400 U2HC) and a conveyor belt speed of 10 m / min under a nitrogen atmosphere (O 2 not more than 500 ppm). The radiation dose was about 3800 mJ / cm ² . The higher the value for the end-of-stroke damping, the higher the hardness.

The Erichsen depression was determined analogously to DIN 53156. For this purpose, the particular preparation according to the invention with a wet film thickness of 200 μm was applied to BONDER sheet 132 by means of a box doctor blade. For curing was exposed in the manner described above. Subsequently, the Erichsen depression was determined by pressing a metal ball into the uncoated side of the sheet. High values mean high flexibility.

Scratch resistance was determined using the Scotch Brite test after storage for 7 days in a climate chamber. In the Scotch-Brite test, a 3 × 3 cm silicon carbide-modified fiber fleece (Scotch Brite SUFN, 3M company) is attached to a cylinder as test specimen. This presses the fiber fleece with 750 g to the coating and is pneumatically moved over the coating. The distance of the deflection is 7 cm. After 10 or 50 double strokes (DH), the gloss (eight-fold determination) is measured analogously to DIN 67530 at an incident angle of 20 ° in the middle region of the stress. The residual gloss value in percent results from the ratio of gloss after load to initial gloss. After 50 double strokes, gently wipe twice with a soft cloth soaked in benzene and measure the residual shine again. Subsequently, the reflow is determined after 2 h at 80 ° C in a drying oven by measuring the residual gloss. The radiation-curable composition was prepared by intensive mixing of 100 parts by weight of the urethane acrylates obtained under Examples 3 and 4 or Comparative Example 1 with 4 parts by weight of 1-hydroxycyclohexyl-phenylketone (commercial photoinitiator Irgacure® 184 from Ciba Spezialitätenchemie).

Application test 2: Demonstration of the self-healing effect by DMTA measurements

The radiation-curable composition was prepared by intensive mixing of 100 parts by weight of the urethane acrylates obtained under Example 3 or Comparative Example 1 with 4 parts by weight of 1-hydroxycyclohexyl-phenylketone (commercial photoinitiator Irgacure® 184 from Ciba Spezialitätenchemie). The radiation-curable compositions were applied to glass using a box wiper with a wet film thickness of 100 μm. The wet films were first flashed for 15 minutes at 23 ° C and then dried at 100 ° C for 20 minutes. The curing of the films obtained in this way was carried out on an IST coating system (type M40 2x1 -R-IR-SLC-So inert) with 2 UV lamps (high-pressure mercury lamps type M 400 U2H and type M 400 U2HC) and a conveyor belt speed of 10 m / min under a nitrogen atmosphere (O 2 not more than 500 ppm). The radiation dose was about 3800 mJ / cm ² .

The determination of the dynamic mechanical behavior of the thus prepared free final cured films with a layer thickness of 50-70 microns was carried out by dynamic mechanical thermal analysis (DMTA) at a heating rate of 2 ° C / min and a frequency of 1 Hz The temperature range of the DMTA measurement was -30 ° C to 200 ° C with the temperature maintained at 150 ° C for 60 min (Instrument: Rheometrics Solids Analyzer RSA II; Sample Geometry: Long: 34.5 mm, Width: 6 , 0 mm, thickness 0.051 mm to 0.071 mm). In the coating based on the silyl group-containing urethane acrylate prepared in Example 3, a maximum of the tan δ at 90 ° C was measured. In the rubber-elastic range (T> 120 ° C, storage modulus 10 ⁸ Pa) was shown from 150 ° C, a lowering of the storage modulus (modulus of elasticity) to 10 ⁵ Pa at 200 ° C. This shows the chemical cleavage of the network, which is responsible for the self-healing effect.

The coating based on the urethane acrylate from Comparative Example 1 did not show this behavior. A maximum of tan δ at 65 ° C was measured. The storage modulus in the rubber-elastic range (T> 80 ° C) was 10 ⁸ Pa in the temperature range up to 200 ⁰ C.

Claims

claims

1. coating compositions containing as structural components

(A) at least one compound which has at least one silicon atom and at least one isocyanate-reactive group (Y), the reaction product is easily cleaved back with isocyanate, as the corresponding reaction product with a compound having primary hydroxyl groups, and optionally at least one further isocyanate-reactive Group (Z) other than (Y) as well as

(B) at least one optionally blocked di- or polyisocyanate.

2. Coating composition according to claim 1, characterized in that the isocyanate-reactive groups (Y) are selected from the group consisting of phenols, imidazoles, triazoles, pyrazoles, oximes, N-hydroxyimides, hydroxybenzoic acid esters, secondary amines, lactams, CH-acid cyclic ketones, malonic esters and alkyl acetoacetates.

3. Coating composition according to one of the preceding claims, characterized in that the compound (A) contains 2 to 20 groups (Y).

4. Coating composition according to one of the preceding claims, characterized in that up to 5 mol / kg of compound (A) groups (Y) in the compound (A) are contained.

5. Coating composition according to one of the preceding claims, characterized in that the compound (A) has 1 to 50 silicon atoms.

6. Coating composition according to one of the preceding claims, characterized in that the compound (A) is obtainable by reacting at least one compound (A1) which has at least one silicon atom and at least one Si-H group with at least one compound (A2), which carries at least one group (Y) and at least one vinylic group.

7. Coating composition according to claim 6, characterized in that the

Compound (A1) has the formula (II)

or formula (IM)

wherein

R ² are independently hydroxy (-OH), Ci - Cis-alkyl, Cβ - Ci2-aryl, Cs - C ^ cycloalkyl, Ci - Cis-Alkoky and _C6 - _Ci2 aryloxy,

can mean.

8. Coating composition according to claim 6 or 7, characterized in that the compound (A2) has the formula (IV),

Vin-R ⁴ -Y

wherein

Vin a vinyl group,

R ^{4 is} a single bond, an oxygen atom, a nitrogen atom, C1-C20-

Alkylene, C6-Ci2-arylene, C3-Ci2-cycloalkylene, or by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups and / or by one or more - (CO) -, - 0 (CO) O-, - (NH) (CO) O-, -O (CO) (NH) -, -O (CO) - or - (CO) O- groups interrupted C2-C2o-alkylene and

Y is a group (Y)

mean.

9. Coating composition according to claim 6 or 7, characterized in that the compound (A2) has the formula (VI),

wherein

Vin a vinyl group,

R ^{5 represents} a single bond, an oxygen atom, a nitrogen atom or C 1 -C 20 -alkylene,

R ^{6 are} each independently of the same x identical or different radicals selected from the group consisting of hydroxy (-OH), C 1 -C 20 -alkyl, d-

C2o-alkyloxy and C6-Ci2-aryloxy and

x is an integer from 0 to 4

mean.

10. Use of coating compositions according to one of claims 1 to 9 for the production of coatings which have a reparable by energy input effect.

1 1. A coating obtainable by mixing and reaction of binder components (A) and (B) according to any one of claims 1 to 9.

12. A coating according to claim 1 1, characterized in that it has a glass transition temperature of -30 to 120 ° C.

13. A process for the thermal treatment of coatings according to any one of claims 1 1 to 12, characterized in that the coatings are heated for a period of at least 10 minutes to a temperature which is at least 25 ° C above the glass transition temperature of the coating.

14. The method according to claim 13, characterized in that one heats with NIR radiation.

15. Compounds of the formulas

such as

wherein

R ² independently of one another are hydroxy (-OH), C 1 -C ₆ -alkyl, C ₆ -C 12 -aryl, C ₁ -C 12 -cycloalkyl, C ₁ -C ₆ -alkoxy and C ₆ -C 12 -aryloxy,

R ^{4 is} a single bond, an oxygen atom, a nitrogen atom, C 1 -C 20 -alkylene, C 6 -C 12 -arylene, C 3 -C 12 -cycloalkylene, or by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted Imino groups and / or by one or more - (CO) -, -O (CO) O-, - (NH) (CO) O-, -O (CO) (NH) -, -O (CO) - or - (CO) O groups interrupted C2-C2o-alkylene,

R ^{5 is} a single bond, an oxygen atom, a nitrogen atom or C 1 -C 20 -alkylene R ^{6 are} each independently of the same x identical or different radicals selected from the group consisting of hydroxy (-OH), C 1 -C 20 -alkyl, d-

C2o-alkyloxy and C6-Ci2-aryloxy,

Y is an isocyanate-reactive group whose reaction product is more readily cleavable with isocyanate than the corresponding reaction product with a compound having primary hydroxy groups, n is an integer of 0 to 50, m is an integer of 1 to 50, and x is an integer of O to 4

mean.

16. Use of compounds according to claim 15 as reactants with di- and polyisocyanates.

17. Reaction products obtained by reaction of compounds according to claim 15 with di- and polyisocyanates.

18. Use of compounds according to claim 15 or compounds of the formula (Villa) and (VIIIb)

(Villa)

wherein

R ² , R ⁴ , R ⁵ , R ⁶ , Y, n and x may have the meanings given in claim 15,

as protecting groups for isocyanate group-containing compounds.

19. Reaction products (G) of compounds (A), according to claim 1, having at least one at least one isocyanate group-containing isocyanate compound.

20. Compounds (G) according to claim 19, characterized in that the isocyanate compound is selected from the group consisting of diisocyanates, isocyanurate group-containing polyisocyanates and allophanate-containing polyisocyanates.

21. Compounds of the formulas

(IXa)

(IXc)

(IXd) as well

O

(IXe)

O

(IXf)

and

(IXG).

wherein

the variables R ² , R ⁴ , R ⁵ , R ⁶ , n, m, x and Y as in the preceding claims,

R ^{12 is} an aromatic, aliphatic or cycloaliphatic organic bivalent radical comprising 2 to 20 carbon atoms, R ^{13 is} an aliphatic or cycloaliphatic bivalent radical having 1 to 8 carbon atoms, R ^{14 is} hydrogen or methyl and q is a positive whole or randomly fractured real one Number of at least 1 mean.

22. Reaction products (H) of compounds (G) according to claim 19 with compounds which have at least one isocyanate-reactive group and at least one free-radically polymerizable group.

23. Compounds (H) according to claim 22, characterized in that the isocyanate-reactive group is hydroxy (-OH).

24. Compounds (H) according to claim 22 or 23, characterized in that the at least one radically polymerizable group is selected from the group consisting of vinyl ether groups, acrylate groups and methacrylate groups.

25. Compounds (H) according to any one of claims 22 to 24, characterized in that the compounds which contain at least one isocyanate reactive group and at least one radically polymerizable group selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1, 4-butanediol mono (meth) acrylate, neopentylglycol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, glycerol mono- and di (meth) acrylate, trimethylolpropane mono- and di (meth) acrylate, Pentaerythritol mono-, di- and tri (meth) acrylate and also 4-hydroxybutyl vinyl ether, 2-aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 4-aminobutyl (meth) acrylate, 6-aminohexyl (meth) acrylate, 2-thioethyl (meth) acrylate, 2-aminoethyl (meth) acrylamide, 2-aminopropyl (meth) acrylamide, 3-aminopropyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, 2- Hydroxypropyl (meth) acrylamide and 3-hydroxypropyl (meth) acrylamide.

26. Compounds of the formulas

(Xa)

(Xb)

(Xc)

(Xd) as well

(Xe)

(Xf) (Xg)

wherein the variables are defined as in the preceding claims.

27. Use of the compounds (G) according to any one of claims 19 - 22 in one or two-component polyurethane coatings.

28. Use of the compounds (H) according to any one of claims 23 - 26 in the radiation curing and in radiation-curable coatings.